CN109921037A - A kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction - Google Patents
A kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction Download PDFInfo
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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
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Abstract
The invention belongs to electro-catalysis technical fields, and in particular to a kind of for the Fe/N/C codope method for preparing catalyst of efficient oxygen reduction reaction and its application.It, which is synthesized, mainly passes through two steps of hydro-thermal reaction and high temperature pyrolysis, the first step is that carbon black, glucose, lauryl sodium sulfate and molysite are dissolved in secondary water, by being ultrasonically formed unit for uniform suspension, then mixed solution is placed in progress hydro-thermal reaction in reaction kettle and obtains black solid powder, i.e. presoma；In second step, presoma is sufficiently mixed according to a certain percentage with nitrogen source, high-temperature calcination in a nitrogen atmosphere obtains Fe/N/C codope catalyst.Prepared catalyst can see apparent active particle and more uniformly be doped in carbon skeleton, related Electrochemical results show that the catalyst can be with the oxygen reduction reaction (ORR) in efficient catalytic alkaline medium, half wave potential reaches 821 mV(relative to reversible hydrogen electrode) it is slightly below the 857mV of business Pt/C, while there is the stability and methanol tolerance performance better than the latter.
Description
Technical field
The invention belongs to electro-catalysis technical fields, and in particular to a kind of Fe/N/C codope for efficient oxygen reduction reaction
Method for preparing catalyst and its application.
Background technique
Fuel cell as a kind of new green energy resource mode, due to its have the characteristics that efficiently, it is environmentally friendly increasingly by
The common concern of people.Occur in the oxygen reduction process (ORR) of fuel battery negative pole to be a highly important half-reaction, but
Its kinetics slowly significantly limits the efficiency of fuel cell.Currently, platinum and its alloy catalyst are considered as performance
Optimal ORR catalyst, but the factors such as it is expensive, reserves are low the large-scale commercial application of fuel cell is caused it is huge
Big limitation.Therefore, the novel cheap non-precious metal catalyst with excellent properties is designed and developed to replace platinum based catalyst
Just seem very it is necessary to.
The base metals such as Fe, Co, Ni and its compound rich reserves in nature, it is cheap and be easy to get, in recent years
Research shows that non-precious metal catalyst shows the excellent ORR performance for the noble metal that can match in excellence or beauty, become building ORR fuel cell yin
The important component of electrode catalyst.Wherein, one or more heterogeneous element (N, S, B, P are introduced in non-precious metal catalyst
Deng) its catalytic activity and stability can be effectively promoted, being substantially improved for performance may be from their unique electronics knots
Structure and the more active sites being exposed by regulating and controlling pattern, make it easier to the reduction of catalytic oxygen, reduce reaction energy
It builds.Since carbon nanomaterial (carbon black, carbon nanotube, carbon nano-fiber, graphene and nano-porous structure carbon etc.) is with excellent
Electric conductivity and big specific surface area, therefore suitable carbon material would generally be added during the preparation process as skeleton and conductive base
Bottom.But the preparation methods of most of reports are complex, and it is simple and have excellent performance to develop a kind of preparation process in this context
Base metal ORR catalyst is with regard to particularly necessary.
The present invention be successfully prepared by way of hydro-thermal and high temperature pyrolysis under alkaline condition have excellent catalytic activity,
The Fe/N/C codope catalyst of stability and methanol tolerance performance, the preparation method is simple and convenient, and raw material is easy to get.
Summary of the invention
To solve the above problems, an object of the present invention is to provide a kind of Fe/N/C codope elctro-catalyst preparation side
Method, this method preparation process is simple, raw material is easy to get and inexpensively, has practical application potentiality.
The second object of the present invention is to provide the application of the Fe/N/C codope elctro-catalyst, that is, it is used for the yin of fuel cell
Pole hydrogen reduction process, the ORR take-off potential relative to reversible hydrogen electrode are 0.963V, half wave potential 0.821V, through durable
Property test after half wave potential only reduce 7mV, be provided simultaneously with excellent methanol tolerance performance.
To achieve the above objectives, the specific technical solution that the present invention takes are as follows:
1. a kind of preparation method of the Fe/N/C codope elctro-catalyst for efficient oxygen reduction reaction comprising the steps of:
(1) by 1.0 g carbon blacks, (XC-72, specific surface area are 235 m2 g-1) be put into 6 mol/L nitric acid solutions, heating water bath,
Flow back 48 h at 80 DEG C, then filters, and secondary water washing three times, is put in a vacuum drying oven, and 60 DEG C of drying are fully ground
It is placed in spare at dry.
(2) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml
In secondary water, 4 h are ultrasonically treated, uniform black suspension is formed, ferric nitrate is then added, transfer the solution into hydro-thermal reaction
In kettle, setting oven temperature be 180 DEG C, the reaction time be 15 h, naturally cool to room temperature, filter, secondary water washing three times,
It is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(3) it takes above-mentioned black powder sample (intermediate product) and melamine to be sufficiently mixed to be placed in tube furnace, nitrogen
High temperature pyrolysis under atmosphere obtains black solid powder.
The additional amount of step (2) described ferric nitrate is 0.5 ~ 1.5 mmol；
Mass ratio 1:5 ~ 10 of step (3) intermediate product and melamine；
Pyrolysis temperature is 800 ~ 1000 DEG C under step (3) described nitrogen atmosphere, and pyrolysis time is 1 h, heating rate 10
℃/min。
2. with a kind of answering for Fe/N/C codope elctro-catalyst for efficient oxygen reduction reaction of above-mentioned steps preparation
With steps are as follows:
Hydrogen reduction (ORR) performance test is carried out on electrochemical workstation to be coated with using the three-electrode system of standard
The glass-carbon electrode of Fe/N/C codope elctro-catalyst is working electrode, and platinum plate electrode is to electrode, and calomel electrode is reference electrode；
0.1mol/L potassium hydroxide solution is electrolyte；Five mouthfuls of glass electrolytic cells of tradition are reaction unit.Test result shows that it is opposite
It is 0.963V in the ORR take-off potential of reversible hydrogen electrode, half wave potential 0.821V, half wave potential only drops after durability test
Low 7mV is provided simultaneously with excellent methanol tolerance performance.
The glass-carbon electrode coated with Fe/N/C codope elctro-catalyst the preparation method is as follows:
5mg Fe/N/C codope elctro-catalyst powder is weighed, is added in 0.5ml aqueous isopropanol, ultrasonic disperse 1h is obtained
Uniform black slurries extract 10 μ l slurries with microsyringe, coated on clean glassy carbon electrode surface, then take 10 μ l
Nafion solution (Nafion solution of 10 μ l, 0.5 wt. % is dissolved into 1.0ml isopropanol) is coated in catalyst surface, red
It is dried under outer lamp to get the glass-carbon electrode coated with Fe/N/C codope elctro-catalyst is arrived.
Beneficial achievement of the invention:
The present invention provides a kind of preparation method of Fe/N/C codope elctro-catalyst and its in fuel cell oxygen reduction
Using, compared with other oxygen reduction catalysts, with simple, the cheap feature of preparation process, at the same with traditional quotient
Industry Pt/C catalyst is compared, catalytic performance can compare favourably therewith, half wave potential relative to the only low 36mV of reversible hydrogen electrode,
It is better than Pt/C catalyst in durability and methanol tolerance aspect of performance.These excellent performance gains are in the codope of Fe/N element
It changes the electronic structure of carbon nanomaterial and improves electric conductivity, provided for electronics transfer transmitting in catalytic process good
Channel is conducive to the absorption and disengaging of intermediate product, accelerates mass transfer velocity.Preparation method provided by the present invention is easily achieved
Industrially scalable application has certain meaning to entreprise cost society energy consumption is reduced, also to design and develop base metal oxygen also
Raw catalyst provides new selection.
Detailed description of the invention
Fig. 1: the sample ID prepared under different condition.
Fig. 2: a, b Fe0.5The transmission electron microscope picture of NC-900-2；C, d is Fe1.5The transmission electron microscope picture of NC-900-2；E, f is
Fe2.5The transmission electron microscope picture of NC-900-2.
Fig. 3: a Fe1.5The transmission electron microscope picture of NC-600-2；B is Fe1.5The transmission electron microscope picture of NC-700-2；C is
Fe1.5The transmission electron microscope picture of NC-800-2；D is Fe1.5The transmission electron microscope picture of NC-1000-2.
Fig. 4: line (a-e) is respectively Fe1.5The XRD spectrum of NC-T-2 (T=600,700,800,900,1000),
Line (f-g) is FexNC-900-2(X=0.5,2.5) XRD spectrum.
Fig. 5: Fe1.5NC-900-1、Fe1.5NC-900-2 and Fe1.5The x-ray photoelectron spectroscopy of NC-900-3, a, c and e points
It Wei not corresponding total spectrogram；B, d, f are respectively corresponding N1s spectrogram.
Fig. 6: a Fe0.5NC-900-2、Fe1.5NC-900-2 and Fe2.5The linear sweep voltammetry curve of NC-900-2；B is
Fe1.5NC-600-2、Fe1.5NC-700-2、Fe1.5NC-800-2、Fe1.5NC-900-2、Fe1.5NC-1000-2's and Pt/C is linear
Scan volt-ampere curve；C is Fe1.5NC-900-1、Fe1.5NC-900-2 and Fe1.5The linear sweep voltammetry curve of NC-900-3.
Fig. 7: a Fe1.5Linear sweep voltammetry curve comparison of the NC-900-2 after 1000 circle cyclic voltammetrics；B is Pt/C
Linear sweep voltammetry curve comparison after 1000 circle cyclic voltammetrics；C is Fe1.5NC-900-2 methanol tolerance linear scan
Volt-ampere curve comparison；D is Pt/C methanol tolerance linear sweep voltammetry curve comparison；E is Fe1.5NC-900-2 and Pt/C is used
The methanol tolerance of chronoamperometry compares, f Fe1.5NC-900-2 and Pt/C linear scan after 1000 circle cyclic voltammetrics
Volt-ampere curve comparison.
Specific embodiment
The present invention is further made explanations and illustrated below by way of specific embodiment and in conjunction with attached drawing.
Carbon black used in embodiment (XC-72) before the use, passes through following pretreatment: by 1.0 g carbon black (XC-
72, specific surface area is 235 m2 g-1) be put into 6 mol/L nitric acid solutions, heating water bath, flow back 48 h at 80 DEG C, then
Filter, secondary water washing three times, puts in a vacuum drying oven, 60 DEG C of drying, be fully ground be placed in it is spare at dry.
Embodiment 1:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 0.5 mmol ferric nitrate is then added, transfers the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as0.5NC-900-2。
Embodiment 2:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-900-2。
Embodiment 3:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 2.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as2.5NC-900-2。
Embodiment 4:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 600 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-600-2。
Embodiment 5:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 700 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-700-2。
Embodiment 6:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 800 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-800-2。
Embodiment 7:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 800mg melamine to be sufficiently mixed and is placed on tube furnace
In, the mass ratio of the two is 1:10, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 1000 DEG C, 1 h of time, and heating rate is
10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-1000-2。
Embodiment 8:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 400 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:5, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, and heating rate is
10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-900-1。
Embodiment 9:
(1) the pretreated carbon black of 40 mg, 1.60 g glucose are taken, 20 mg dodecyl sodium sulfates are dissolved into 20 ml bis- times
In water, 4 h are ultrasonically treated, uniform black suspension is formed, 1.5 mmol ferric nitrates is then added, transfer the solution into hydro-thermal
In reaction kettle, setting oven temperature is 180 DEG C, and the reaction time is 15 h, naturally cools to room temperature, is filtered, secondary water washing three
It is secondary, it is dried at 60 DEG C of vacuum oven, obtains black powder after being fully ground.
(2) it takes 80 mg black powder samples (intermediate product) and 1200 mg melamines to be sufficiently mixed and is placed on tubular type
In furnace, the mass ratio of the two is 1:15, and high temperature pyrolysis under nitrogen atmosphere, pyrolysis temperature is 900 DEG C, 1 h of time, heating rate
For 10 DEG C/min, black solid powder is obtained, Fe is denoted as1.5NC-900-3。
As shown in Figure 1, listing the preparation condition difference of different samples in order to distinguish.
As shown in Fig. 2, carbon black degree of overlapping is higher in Fig. 2 a shows velveteen shape, apparent active particle is not observed, only
There is black reunion, can be seen that atomic arrangement is very chaotic by Fig. 2 b, spacing of lattice is shown as 0.209 nm；With molysite forerunner
The increase of object, the clear spacing of lattice of atomic arrangement are 0.206 nm, the Fe for being 0.204 nm very close to spacing of lattice3N's
(111) crystal face；When molysite increases to 2.5 mmol, formed there are many non-uniform bulk metal compound, spacing of lattice is
0.298 nm, corresponding Fe2O3(220) crystal face.
As shown in figure 3, the catalyst sample pattern prepared under different pyrolysis temperatures is significantly different, with pyrolysis temperature
Increased activity amounts of particles gradually increases and more uniformly, but occurs when pyrolysis temperature is increased to 1000 DEG C non-uniform big
Block metallic compound.
As shown in figure 4, XRD diffraction maximum corresponds respectively to Fe at 29.7 °, 40.8 °, 43.4 °, 57.0 °3N(PDF#49-
1662) (101), (002), (111), (112) crystal face and the peak detected at 30.2 °, 35.6 °, 57.3 °, 62.9 ° difference
Corresponding to Fe2O3(PDF#39-1346) (220), (311), (422), (440) crystal face, the phenomenon table in conjunction with shown in Fig. 2 and Fig. 3
The bright catalyst is made of carbon, iron oxide and nitrided iron.
As shown in figure 5, Fig. 5 a, 5c and 5e are Fe respectively1.5NC-900-1, Fe1.5NC-900-2 and Fe1.5NC-900-3
The total spectrogram of XPS, further demonstrate the catalyst and be made of C, N, O and Fe element；By comparing the N1s of three kinds of catalyst
Map, it can be seen that in five kinds of different type nitrogen, graphite nitrogen and nitrogen " iron " account for 40 ~ 60%, and the nitrogen of both types exists
Fe1.5Other two kinds of catalyst are apparently higher than in NC-900-2, this may be the weight for causing the catalyst to have excellent properties
Want reason.
As shown in fig. 6, compared with other catalyst, Fe1.5NC-900-2 shows optimal catalytic activity, with business
Pt/C catalyst is compared, and only low 30 mV has reached 821 mV(relative to reversible hydrogen electrode to half wave potential).
As shown in fig. 7, Fig. 7 a is shown in after the CV test of 1000 circles, Fe1.5NC-900-2 half wave potential reduced by only
Half wave potential is greatly reduced business Pt/C catalyst under identical testing conditions in 7 mV, Fig. 7 b, reaches 60 mV, will test
Linear volt-ampere curve afterwards compares (Fig. 7 f), it can be seen that Fe1.5The half wave potential of NC-900-2 is higher by than business Pt/C
18 mV；Fig. 7 c and 7d are Fe respectively1.5The methanol tolerance performance test of NC-900-2 and business Pt/C, comparing result show prepared
Fe1.5There is NC-900-2 excellent methanol tolerance performance to adopt simultaneously to further prove the methanol tolerance performance of the catalyst
It is tested (Fig. 7 e) with i-t method, as the result is shown Fe1.5Fluctuation NC-900-2 only small after methanol is added dropwise, 1000
Still maintain 92% electric current after s, and business Pt/C fluctuation, electric current is only 54% at the end of test.These test results are equal
Show Fe1.5NC-900-2 has excellent ORR catalytic performance.
Claims (9)
1. a kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction, feature exist
In: the method for high temperature pyrolysis makes the compounds such as FeN more uniformly be doped to carbon black under by hydro-thermal reaction and inert gas
Grain surface.
2. a kind of Fe/N/C codope elctro-catalyst preparation method and applications for efficient oxygen reduction reaction, feature exist
In, include following preparation step: by Jing Guo nitric acid pretreatment carbon black and Fe (NO3)3•9H2O, glucose and dodecyl sodium sulfonate
Sodium is ultrasonically treated in the beaker containing secondary water, is formed unit for uniform suspension, is subsequently poured into reaction kettle and carries out hydro-thermal reaction, to
After naturally cooling to room temperature, through suction filtration, washs, is dried to obtain iron content presoma, by the iron content presoma and melamine of preparation
It is sufficiently mixed and is placed in tube furnace, high temperature pyrolysis is carried out under nitrogen atmosphere protection, obtains final products.
3. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
It is applied, it is characterised in that: the preprocessing process of carbon black is as follows: taking appropriate carbon black in 6M nitric acid, flow back 48h at 80 DEG C.
4. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
It is applied, it is characterised in that: the addition Fe (NO3)3•9H2The molal quantity of O is 0.5-2.5mmol.
5. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
It is applied, it is characterised in that: the sonication treatment time is 4h.
6. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
It is applied, it is characterised in that: hydrothermal temperature is 180 DEG C, reaction time 15h.
7. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
It is applied, it is characterised in that: iron content presoma is 1:5-15 with melamine mass ratio.
8. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
Its apply, it is characterised in that: pyrolysis temperature be 600-1000 DEG C, pyrolysis time 0.5-2h, pyrolysis rate be 10 DEG C/
min。
9. a kind of Fe/N/C codope elctro-catalyst preparation method for efficient oxygen reduction reaction as claimed in claim 2 and
It is applied, it is characterised in that: is applied to the oxygen reduction reaction under alkaline condition as effective catalyst.
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| CN112421060A (en) * | 2019-08-20 | 2021-02-26 | 中国科学院大连化学物理研究所 | Nitrogen-doped ferrous sulfide iron oxide reduction catalyst material and preparation application thereof |
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| CN113054210A (en) * | 2021-03-22 | 2021-06-29 | 中南大学 | Oxygen reduced iron-iron nitride @ monoatomic iron and nitrogen co-doped amorphous carbon-carbon black composite catalyst and preparation and application thereof |
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| CN113054210B (en) * | 2021-03-22 | 2024-04-16 | 中南大学 | Oxygen reduced iron-ferroferric nitride @ monoatomic iron and nitrogen co-doped amorphous carbon-carbon black composite catalyst and preparation and application thereof |
| CN113629261A (en) * | 2021-07-09 | 2021-11-09 | 江苏科技大学 | Morphology-controllable pentairon di-carbide/ferric oxide/iron-nitrogen-carbon electrocatalyst and preparation method thereof |
| CN113629261B (en) * | 2021-07-09 | 2022-08-19 | 江苏科技大学 | Morphology-controllable pentairon di-carbide/ferric oxide/iron-nitrogen-carbon electrocatalyst and preparation method thereof |
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