CN107742732B - A kind of iron content oxygen reduction catalyst and its preparation method and application - Google Patents
A kind of iron content oxygen reduction catalyst and its preparation method and application 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
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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
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Abstract
The present invention provides a kind of preparation method of iron content oxygen reduction catalyst, belongs to field of catalyst preparation.The present invention is ground after soluble ferric iron salt, KB, itrogenous organic substance and water are mixed progress hydro-thermal reaction, then carries out the first calcining, and the first calcined product carries out the second calcining after inorganic acid elution, obtains iron content oxygen reduction catalyst.The present invention uses inexpensive raw material, and iron content oxygen reduction catalyst is prepared using the process flow that can be mass-produced, and reduces production cost, while the iron in soluble ferric iron salt being dispersed in KB, and obtain the carbon (N of N doping simultaneouslyxCy) and FeNxCyActive site and Fe7C3And Fe3N nano particle, conductive black KB supported active site and nano particle, and then its catalytic performance can be promoted.Embodiment statistics indicate that, iron content oxygen reduction catalyst prepared by the present invention is very close to the performance for the platinum carbon catalyst that the catalytic performance of oxygen reduction reaction and commercial content are 20%.
Description
Technical field
The present invention relates to catalyst preparation technical fields more particularly to a kind of iron content oxygen reduction catalyst and preparation method thereof
And application.
Background technique
Metal-air battery especially aluminium-air cell is most promising energy conversion and storing technology means.Aluminium
Air cell has many features, for example price is low, and environmental-friendly, running temperature is low (room temperature), and actual energy density is up to
600wh·kg-1.But the reaction speed of the air electrode of aluminium-air cell at normal temperature is very slow, needs catalyst to be catalyzed
Speed-raising.Catalyst best at present is business platinum carbon, it can be common that JM 20%Pt/C, but platinum is very expensive, and dilute
It is few, it is difficult business application on a large scale.Therefore, the bottleneck problem that efficient non-platinum metal catalyst has become the battery is found.
In recent years, the carbon material of carbon material especially N doping modifies the catalysis of the active particle containing transition metal simultaneously
Agent is widely noticed, and especially nitrogen and iron modifies the catalyst of carbon material (Fe-N-Cs) type of doping jointly (oxygen is also in ORR
Original reaction) in terms of research achieve relatively good achievement.Researcher is it is believed that be wrapped in non-in graphited carbon material
The FeN of crystalline statexCyIt is the chief active site of such catalyst with the iron-based nano particle of crystalline state.Currently, preparation Fe-N-C class
The common technique scheme of catalyst is summed up as follows: (1) mixing molysite with itrogenous organic substance, while adding soft template such as P123
(polyoxyethylene-poly-oxypropylene polyoxyethylene block copolymer) or F127 (polyox-yethylene-polyoxypropylene block copolymer),
Or silicon dioxide hard template, the regular hour is calcined under argon gas stream；(2) ferriporphyrin is made in molysite and porphyrin or phthalein blueness
Perhaps iron phthalein is green or molysite and carbon containing itrogenous organic substance are mixed and made into iron organic framework compounds, then calcines centainly
Time.But these preparations often require to use the more expensive material of price, such as soft template P123, F127, silica, iron phthalein
There are expensive starting materials in blueness, porphyrin etc..
Summary of the invention
In view of this, not influenced the purpose of the present invention is to provide a kind of preparation method of iron content oxygen reduction catalyst
The cost of raw material is reduced on the basis of the catalytic activity of oxygen reduction catalyst.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of preparation method of iron content oxygen reduction catalyst, the iron content oxygen reduction catalyst have chemical group shown in Formulas I
At:
Fe7C3-Fe3N/FeNxCy- KB Formulas I,
KB is conductive black in Formulas I；
The preparation method comprises the following steps:
(1) soluble ferric iron salt, KB, itrogenous organic substance and water are mixed and carries out hydro-thermal reaction, obtain hydrothermal product；
(2) hydrothermal product that the step (1) obtains is ground, obtains grinding material；
(3) step (2) is obtained into grinding material and carries out the first calcining, obtain the first calcined product；
(4) the second calcining is carried out after washing the first calcined product that the step (3) obtains in mineral acid, is contained
Iron oxygen reduction catalyst.
Preferably, the temperature of hydro-thermal reaction is 100~120 DEG C in the step (1), and the time of the hydro-thermal reaction is 12
~for 24 hours.
Preferably, in the step (1) in soluble ferric iron salt in the mole of iron and itrogenous organic substance N element mole
Mass ratio with KB is 4mmol:7~10mmol:0.2g.
Preferably, before grinding material carries out the first calcining in the step (3) further include: wrap up the abrasive material with copper foil
Material.
Preferably, the temperature of the first calcining is 600~900 DEG C in the step (3), and the time of first calcining is 1
~3h.
Preferably, in the step (4) second calcining temperature be 600~900 DEG C, it is described second calcining time be
0.5~2h.
Preferably, the mass concentration of inorganic acid is 3mol/L in the step (4), the first calcined product when the washing
Quality and the volume ratio of inorganic acid are 3g:60~70mL.
The present invention also provides iron content oxygen reduction catalyst made from preparation method described in above-mentioned technical proposal, the iron content
Oxygen reduction catalyst includes the element of following mass percentage: C:90~96.31%, and Fe0.66~2%, N 2.08~
2.5%.
Preferably, the partial size of the iron content oxygen reduction catalyst is 30~82nm.
The present invention also provides application of the iron content oxygen reduction catalyst in oxygen reduction reaction described in above-mentioned technical proposal.
The present invention provides a kind of preparation method of iron content oxygen reduction catalyst, iron content oxygen reduction catalyst has Formulas I institute
Show chemical composition: Fe7C3-Fe3N/FeNxCy- KB Formulas I, KB is conductive black in Formulas I, by soluble ferric iron salt, KB, itrogenous organic substance
And ground after water mixing progress hydro-thermal reaction, the first calcining is then carried out, the first calcined product washs laggard in mineral acid
Row second is calcined, and iron content oxygen reduction catalyst is obtained.The present invention uses inexpensive raw material, can be mass-produced using mild
Process flow prepares iron content oxygen reduction catalyst, reduces production cost, while the iron in soluble ferric iron salt is evenly dispersed
In KB, and the carbon (N of N doping is obtained simultaneouslyxCy) and FNxCyActive site and Fe7C3And Fe3N nano particle, conductive charcoal
Black KB loads these active sites and nano particle, and then can promote its catalytic performance.Embodiment statistics indicate that, the present invention
The platinum carbon catalyst that the iron content oxygen reduction catalyst of preparation is 20% to the catalytic performance of oxygen reduction reaction and commercial content
Performance is very close.
Further, the present invention improves calcine technology, and grinding material is wrapped up before carry out first is calcined with copper foil,
Improve low yield problem caused by calcined gas escapes.Embodiment statistics indicate that: iron content hydrogen reduction provided by the invention
The yield of iron content oxygen reduction catalyst is up to 94% in the preparation method of catalyst.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is Fe made from the embodiment of the present invention 17C3-Fe3N/FeNxCy- KB catalyst is linearly swept with JM 20%Pt/C's
Retouch volt-ampere curve (LSV curve)；
Fig. 2 is Fe made from the embodiment of the present invention 17C3-Fe3N/FeNxCy- KB catalyst and JM 20%Pt/C are at 2000
Recycle the LSV curve of front and back；
Fig. 3 is (a), (b) is Fe made from the embodiment of the present invention 17C3-Fe3N/FeNxCyThe transmission electron microscope picture of-KB, (c),
(e) and (f) be (b) acceptance of the bid circle enlarged drawing, be (d) high angle annular dark；
Fig. 4 is Fe made from the embodiment of the present invention 17C3-Fe3N/FeNxCyThe photoelectron of the N 1s (a) and Cu 2p (b) of-KB
Energy spectrum diagram；
Fig. 5 is Fe made from the embodiment of the present invention 17C3-Fe3N/FeNxCy- KB and 20%Pt/C make in aluminium-air cell
Constant current discharge curve when for cathod catalyst.
Specific embodiment
The present invention provides a kind of preparation method of iron content oxygen reduction catalyst, the iron content oxygen reduction catalyst has formula
Chemical composition shown in I:
Fe7C3-Fe3N/FeNxCy- KB Formulas I,
KB is conductive black in Formulas I；
The preparation method comprises the following steps:
(1) soluble ferric iron salt, KB, itrogenous organic substance and water are mixed and carries out hydro-thermal reaction, obtain hydrothermal product；
(2) hydrothermal product that the step (1) obtains is ground, obtains grinding material；
(3) step (2) is obtained into grinding material and carries out the first calcining, obtain the first calcined product；
(4) the second calcining is carried out after washing the first calcined product that the step (3) obtains in mineral acid, is contained
Iron oxygen reduction catalyst.
Soluble ferric iron salt, KB, itrogenous organic substance and water are mixed and carry out hydro-thermal reaction by the present invention, obtain hydrothermal product.
In the present invention, the mole of N element and the mass ratio of KB in the mole of iron and itrogenous organic substance in the soluble ferric iron salt
Preferably 4mmol:7~10mmol:0.2g, more preferably 4mmol:8mmol:0.2g.
In the present invention, the mole of the soluble ferric iron salt and the volume ratio of water are preferably 4mmol:60~80mL, more
Preferably 4mmol:80mL.
In the present invention, the soluble ferric iron salt preferably includes one of ferrous sulfate, frerrous chloride and ferrous nitrate
Or several mixtures, two kinds of mixture more preferably in ferrous sulfate, frerrous chloride and ferrous nitrate.When the solubility
When molysite is mixture, the present invention does not have special restriction to the ratio of each substance in the mixture.
In the present invention, the itrogenous organic substance preferably includes melamine, octadecylamine, cyanamide, dicyandiamide and polyaniline
One or more of mixture, more preferably two kinds of mixture, the most preferably mixture of melamine and octadecylamine
Or the mixture of melamine and polyaniline.When the itrogenous organic substance is mixture, in the mixture melamine with
The molar ratio of octadecylamine, melamine and polyaniline is independently preferably 1:3.
In the present invention, the specific surface area of the KB is preferably 300~800m2/ g, more preferably 600m2/g.The present invention couple
The source of the KB does not have any special restriction, using commercial goods well known to those skilled in the art.
In the present invention, the temperature of the hydro-thermal reaction is preferably 100~140 DEG C, and more preferably 110~120 DEG C；It is described
The time of hydro-thermal reaction is preferably 12~for 24 hours, more preferably 16~18h.In the present invention, in the hydrothermal reaction process iron with
Melamine is complexed, while itrogenous organic substance can also occur slightly to be carbonized.
The present invention does not have special restriction to the addition sequence of the soluble ferric iron salt, KB, itrogenous organic substance and water, adopts
Solubility is obtained specifically, such as first mixing soluble ferric iron salt with water with charging sequence well known to those skilled in the art
After iron salt solutions, KB and itrogenous organic substance are sequentially added.In the present invention, KB is added to after soluble copper salting liquid preferably
Including mixing, the present invention does not have special restriction to the mixed concrete mode, using well known to those skilled in the art mixed
Conjunction mode, specifically, such as magnetic agitation.After the completion of magnetic agitation, after itrogenous organic substance is added, the present invention is preferably also wrapped
The step of including mixing, the present invention are consistent with the above to the restriction of the hybrid mode, and details are not described herein.
After the completion of hydro-thermal reaction, the present invention is preferably dried product system to obtain hydrothermal product.The present invention is to described
Dry concrete mode does not have special restriction, using drying mode well known to those skilled in the art, specifically, as true
Sky is dry, and the present invention does not have special restriction to the vacuum drying temperature, time and pressure, can remove in product system
Moisture.
The present invention does not have special restriction to the device of the hydro-thermal reaction, specifically, such as hydrothermal reaction kettle.
After obtaining hydrothermal product, the present invention grinds the hydrothermal product, obtains grinding material.In the present invention,
The grinding is levigate by bulky grain hydrothermal product.The present invention does not require the fineness of the grinding material specifically, as long as not having
There is macroscopic bulky grain.The present invention does not have special restriction to the concrete mode of the grinding, preferably in agate
Middle grinding.
After obtaining grinding material, the grinding material is carried out the first calcining by the present invention, obtains the first calcined product.At this
In invention, the temperature of first calcining is preferably 600~900 DEG C, and more preferably 650 DEG C；The time of first calcining is excellent
It is selected as 1~3h, more preferably 2h.In the present invention, during first calcination reaction, not only grinding material is carried out abundant
Carbonization, forms the carbon (N of N dopingxCy) and FNxCyActive site and Fe7C3And Fe3N nano particle.
In the present invention, the calcining preferably carries out in inert gas or nitrogen, and the inert gas is preferably argon gas.
The first calcining is carried out in the present invention, it is preferred to which the grinding material is placed in porcelain boat.
It in the present invention, further preferably include: to wrap up the grinding with copper foil before the step grinding material carries out the first calcining
Material.In the present invention, the first calcined product of part is taken away when the copper foil can prevent gas from escaping, and improves yield.
After obtaining the first calcined product, the present invention carries out second after washing first calcined product in mineral acid and forges
It burns, obtains iron content oxygen reduction catalyst.In the present invention, the mass concentration of the inorganic acid is preferably 3mol/L；Described first
The quality of calcined product and the volume ratio of inorganic acid are preferably 3g:60~70mL, more preferably 3g:70mL.The present invention is to described
The type of inorganic acid does not have special restriction, using inorganic acid well known to those skilled in the art, it is specific such as hydrochloric acid or
Nitric acid.The present invention does not have special restriction to the concrete mode of the inorganic acid elution, it is preferred to use the first calcined product exists
The mode being heated to reflux in inorganic acid is washed.In the present invention, the temperature being heated to reflux is preferably 60~90
DEG C, more preferably 80 DEG C；The time being heated to reflux is preferably 5~7h, more preferably 6h.In the present invention, inorganic pickling
Wash the unstable material that can be dissolved in the first calcined product.
In the present invention, before first calcined product carries out inorganic acid elution further include: by first calcined product
It is cooled to room temperature.The present invention does not have special restriction to the concrete mode of the cooling, and use is well known to those skilled in the art
The type of cooling, specifically, such as natural cooling.
After inorganic acid elution, the present invention is preferably successively filtered, washes, dries and grinds to inorganic acid washed product
Mill.The present invention is filtered inorganic acid washed product to obtain filtration product.In the present invention, the filtering preferably filters.
After obtaining filtration product, the present invention washes filtration product, obtains washing product.The present invention is to the washing
The dosage and washing times of Shi Shui does not have special restriction, can remove the soluble impurity in process product.
After obtaining washing product, the present invention is dried product is washed, and obtains desciccate.The present invention is to the drying
Concrete mode there is no special restriction, can remove washing product in moisture.
After obtaining desciccate, the present invention is preferably ground desciccate to obtain the production for needing to carry out second segment burning
Object.In the present invention, the specifically restriction of the grinding is consistent with the above, and details are not described herein.
In the present invention, the temperature of second calcining is preferably 600~900 DEG C, and more preferably 650 DEG C；Described second
The time of calcining is preferably 0.5~2h, more preferably 1h.In the present invention, gas, device and that second calcining uses
One calcining is identical, and details are not described herein.In the present invention, second calcining can remove remaining inorganic acid, while also to containing
Iron oxygen reduction catalyst has reinforcing at phase separation, and then can be improved the catalytic performance of iron content oxygen reduction catalyst.
The present invention also provides iron content oxygen reduction catalyst made from preparation method described in above-mentioned technical proposal, the iron content
Oxygen reduction catalyst preferably includes the element of following mass percentage: C:90~96.31%, Fe 0.66~2%, N 2.08
~2.5%.In the present invention, the iron content oxygen reduction catalyst further includes the quality percentage of a small amount of impurity element O, the O
Content is preferably 0.95%.
In the present invention, the partial size of the iron content oxygen reduction catalyst is preferably 30~82nm, more preferably 50~60nm.
The present invention also provides application of the iron content oxygen reduction catalyst in oxygen reduction reaction described in above-mentioned technical proposal.
In the present invention, the iron content oxygen reduction catalyst is preferred in aluminium-air cell as cathod catalyst.
Iron content oxygen reduction catalyst provided by the invention and its preparation method and application is carried out below with reference to embodiment detailed
Thin explanation, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
It weighs ferrous sulfate 4mmol to be dissolved in deionized water 80mL, KB 0.2g (specific surface area 300m is added2/ g), magnetic
Power stirs 30 minutes, and melamine 8mmol is added, and continues magnetic agitation 30 minutes, is transferred in 100mL hydrothermal reaction kettle, twists
Tight reaction kettle reacts at 100 DEG C 12 hours, and vacuum filter, dry to anhydrous later.Agate grinding uniformly, is subsequently placed in porcelain boat
In, it is wrapped with pure copper foil, flows down 650 DEG C first in argon gas and calcine 2 hours, cooled to room temperature.Products therefrom is placed in
In the round-bottomed flask of HCl solution equipped with 3mol/L, magnetic agitation flows back 6 hours at 60 DEG C, it is cooling after vacuum filter, go from
Sub- water washing at least 3 times, then sufficiently dry at 80 DEG C to anhydrous, agate grinding uniformly, is subsequently placed in porcelain boat, in argon gas stream
Lower 650 DEG C carry out the second calcining 1 hour, obtain iron content oxygen reduction catalyst (Fe7C3-Fe3N/FeNC-KB).It is computed, iron content
The yield of oxygen reduction catalyst is 94%.
Each element content in iron content oxygen reduction catalyst made from embodiment 1 is analyzed, the results are shown in Table 1.By
Table 1 is as can be seen that after mineral acid treatment, and the content of each element is changed in iron content oxygen reduction catalyst.
Each element content (wt%) in 1 iron content oxygen reduction catalyst of table
Fig. 1 is Fe7C3-Fe3The linear sweep voltammetry curve (LSV) of N/FeNC-KB catalyst and JM 20%Pt/C, horizontal seat
Mark is voltage, and ordinate is the current density (writing a Chinese character in simplified form into j) under corresponding voltage, can compare catalyst from LSV curve
ORR activity size.This curve be to rotate glass-carbon electrode (RDE) as working electrode, it is electric using Ag/AgCl electrode as reference
Pole, platinum electrode is used as to electrode, under the three-electrode system of composition, is 1600 revs/min in the revolving speed of RDE electrode, is utilized electricity
Chem workstation CHI760, the result measured in the KOH solution of the 0.1mol/L of oxygen saturation.It can be seen from figure 1 that Fe7C3-
Fe3The starting voltage of N/FeNC-KB catalyst is in 0.93V or so, and the starting voltage of JM 20%Pt/C is in 0.97V or so, very
Close to the starting voltage of JM 20%Pt/C.Fe7C3-Fe3Limiting current density (the about 6.0mAcm of N/FeNC-KB-2) compare JM
Limiting current density (the about 5.5mAcm of 20%Pt/C-2) want big 0.5mAcm-2.In general, Fe7C3-Fe3N/
FeNC-KB catalyst can compare favourably to the catalytic performance of ORR with JM 20%Pt/C.
In addition, in order to compare catalyst to the active stability of ORR, to catalyst Fe7C3-Fe3N/FeNC-KB and JM
20%Pt/C's has carried out accelerated aging test, i.e., carries out acceleration cyclic test to catalysis, arrives 0.2V voltage range in -0.4V
It is interior, 2000 cyclic voltammetries are carried out in the KOH solution of the 0.1mol/L of oxygen saturation, and detect before and after 2000 circulations
Its LSV curve, with the ORR performance degradation situation of catalyst before and after comparison loop, to understand its stability.2000 circulation front and backs
Result see Fig. 2.Half wave potential refers to voltage corresponding when electric current is the half of carrying current, is denoted as △ E1/2, recycle front and back
Half wave potential difference is denoted as △ E1/2, △ E1/2More small catalyst is more stable.It is clear from fig. 2 that Fe7C3-Fe3N/
The difference △ E of half wave potential of the FeNC-KB before and after 2000 circulations1/2About 8mV is less than JM 20%Pt/C (about
13.3mV), this demonstrate that Fe7C3-Fe3The ORR stability of N/FeNC-KB catalyst is better than JM 20%Pt/C.
(a) is Fe in Fig. 37C3-Fe3The TEM of N/FeNC-KB schemes (transmission electron microscope picture), is (b) its HRTEM figure (high-resolution
Rate transmission electron microscope picture), (c), (e) and (f) be (b) acceptance of the bid circle enlarged drawing.It (d) is HADDF figure (high angle annular dark).
From Fig. 3 (a) as can be seen that the carbon nanotube of diameter about 82nm is distributed in the KB particle of about 50nm, have in carbon nanotube
A little partial size about 30nm iron content particle.It can be seen that from the HRTEM picture of Fig. 3 (c), (e) and (f) and contain nanometer in catalyst
The Fe of grade7C3And Fe3N crystal grain.
Fig. 4 is Fe7C3-Fe3The photoelectron spectroscopy figure of the N 1s (a) and Fe 2p (b) of N/FeNC-KB.It can from Fig. 4 (a)
Out, the photoelectron spectroscopy figure signal of the nitrogen in catalyst can be fitted to four peaks, be respectively in 398.5eV,
400.4eV, 401.4eV and 399.1eV respectively correspond pyridine nitrogen, and pyrroles's nitrogen is graphitized nitrogen and the nitrogen covalent with metal.At this
In, with metal covalent nitrogen-atoms should be with iron covalently, form Fe3N and FeNxCy.From Fig. 4 (b) as can be seen that urging
The photoelectron spectroscopy figure signal of ferro element in agent can be fitted to two peaks, be 711.45eV (Fe 2p3/2, iron) respectively
With 725.05eV (Fe 2p1/2, Fe3+).Complex chart 4 is as can be seen that catalyst Fe7C3-Fe3The ferro element of N/FeNC-KB is main
With iron and Fe3+Form exist, and nitrogen-atoms is then successfully doped into carbon-coating, forms the carbon (N of N dopingxCy) and FeNxCy
Active site.
Fig. 5 is △ E1/2Catalyst Fe7C3-Fe3N/FeNC-KB and 20%Pt/C are urged in aluminium-air cell as cathode
Constant current discharge curve graph when agent, discharge current density 50mAcm-2.From figure 5 it can be seen that Fe7C3-Fe3N/
FeNC-KB shows the discharge voltage plateau of about 1.51V during discharge, and 20%Pt/C is shown during discharge
The voltage platform of about 1.44V.Show that discharge performance of the Cu/CuNC-KB in 10 hours is slightly better than 20%Pt/C.
Embodiment 2
It weighs frerrous chloride 2mmol to be dissolved in deionized water 40mL, KB 0.1g (specific surface area 600m is added2/ g), magnetic
Power stirs 30 minutes, and dicyandiamide 12mmol is added, and continues magnetic agitation 30 minutes, is transferred in 100mL hydrothermal reaction kettle, tightens
Reaction kettle reacts at 120 DEG C 24 hours, and vacuum filter, dry to anhydrous later.Agate grinding uniformly, is subsequently placed in porcelain boat,
It is wrapped with pure copper foil, flows down 700 DEG C first in argon gas and calcine 3 hours, cooled to room temperature.Products therefrom is placed in and is equipped with
In the round-bottomed flask of the HCl60mL solution of 3mol/L, magnetic agitation flows back 6 hours at 80 DEG C, it is cooling after vacuum filter, go from
Sub- water washing at least 3 times, then sufficiently dry at 80 DEG C to anhydrous, agate grinding uniformly, is subsequently placed in porcelain boat, in argon gas stream
Lower 700 DEG C carry out the second calcining 1 hour, obtain iron content oxygen reduction catalyst (Fe7C3-Fe3N/FeNC-KB).It is computed, iron content
The yield of oxygen reduction catalyst is 91%.
Comparative example 1
Using preparation method same as Example 1, without using pure copper foil when difference is only that calcining.It is computed, oxygen is also
The yield of raw catalyst is 12.8%.
Comparative example 2
Using preparation method same as Example 2, without using pure copper foil when difference is only that calcining.It is computed, oxygen is also
The yield of raw catalyst is 11.7%.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of iron content oxygen reduction catalyst, the iron content oxygen reduction catalyst has chemical composition shown in Formulas I:
Fe7C3-Fe3N/FeNxCy- KB Formulas I,
KB is conductive black in Formulas I；
The preparation method comprises the following steps:
(1) soluble ferric iron salt, KB, itrogenous organic substance and water are mixed and carries out hydro-thermal reaction, obtain hydrothermal product；
(2) hydrothermal product that the step (1) obtains is ground, obtains grinding material；
(3) step (2) is obtained into grinding material and carries out the first calcining, obtain the first calcined product；
(4) the second calcining is carried out after washing the first calcined product that the step (3) obtains in mineral acid, obtains iron content oxygen
Reducing catalyst.
2. preparation method according to claim 1, which is characterized in that the temperature of hydro-thermal reaction is 100 in the step (1)
~140 DEG C, time of the hydro-thermal reaction is 12~for 24 hours.
3. preparation method according to claim 1 or 2, which is characterized in that iron in soluble ferric iron salt in the step (1)
The mass ratio of the mole of N element and KB are 4mmol:7~10mmol:0.2g in mole and itrogenous organic substance.
4. preparation method according to claim 1, which is characterized in that grinding material progress first is forged in the step (3)
Before burning further include: wrap up the grinding material with copper foil.
5. preparation method according to claim 1 or 4, which is characterized in that the temperature of the first calcining is in the step (3)
600~900 DEG C, the time of first calcining is 1~3h.
6. preparation method according to claim 1, which is characterized in that the temperature of the second calcining is 600 in the step (4)
~900 DEG C, the time of second calcining is 0.5~2h.
7. preparation method according to claim 1, which is characterized in that the molar concentration of inorganic acid is in the step (4)
3mol/L, the quality of the first calcined product and the volume ratio of inorganic acid are 3g:60~70mL when the washing.
8. iron content oxygen reduction catalyst made from preparation method described in claim 1~7 any one, which is characterized in that described
Iron content oxygen reduction catalyst includes the element of following mass percentage: C:90~96.31%, and Fe0.66~2%, N2.08~
2.5%.
9. iron content oxygen reduction catalyst according to claim 8, which is characterized in that the grain of the iron content oxygen reduction catalyst
Diameter is 30~82nm.
10. application of the iron content oxygen reduction catalyst in oxygen reduction reaction described in claim 8 or 9.
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| CN201710914789.5A CN107742732B (en) | 2017-09-30 | 2017-09-30 | A kind of iron content oxygen reduction catalyst and its preparation method and application |
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| CN108767281A (en) * | 2018-06-28 | 2018-11-06 | 湖南工业大学 | A kind of oxygen reduction catalyst Fe-Mn/N-KB and its preparation method and application |
| CN109921037A (en) * | 2019-03-07 | 2019-06-21 | 曲阜师范大学 | A kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction |
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