CN108281673A - A kind of preparation method of N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst - Google Patents
A kind of preparation method of N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst Download PDFInfo
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- H—ELECTRICITY
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- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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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
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- H01M4/88—Processes of manufacture
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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
- H01M4/96—Carbon-based electrodes
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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 discloses a kind of preparation methods of N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst, by citric acid, urea and graphene oxide ultrasonic dissolution in ultra-pure water, after being uniformly dispersed under 160 ~ 200 oC 10 ~ 13 h of hydro-thermal reaction, after reaction cooled to room temperature.Through being centrifuged off excessive citric acid, urea, it is dried in vacuo 23 ~ 25 h under 40 ~ 60 oC and removes water to get to N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst.Compared with commercialized Pt/C catalyst, N disclosed by the inventionCDots/GO nanocomposites present fabulous electrocatalysis characteristic, there are the initial potential (0.13 V vs.Ag/AgCl) of corrigendum, the current density (reaching 18.4 mA at 0.70 V) of bigger and very excellent electrochemical stability and methanol tolerant or carbon monoxide poisoning；In addition, and NCDots and NCDots/GO mixtures are compared, NCDots/GO nanocomposites also show the catalytic efficiency to compare favourably with commercialized Pt/C catalyst.
Description
Technical field
The invention belongs to the preparing technical fields of carbon nanomaterial, are related to a kind of high catalytic performance N doping carbon dots/oxidation
The preparation method of graphene nano composite electrocatalyst, and in particular to one kind using urea as nitrogen source, citric acid is carbon source, oxidation stone
Black alkene is template, the method for preparing synthesis nitrogen-doped carbon point/stannic oxide/graphene nano composite material using hydro-thermal method.
Background technology
Oxygen reduction reaction (ORR) dynamic process of fuel battery negative pole is very slow, a large amount of precious metals platinum catalyst
Use so that battery cost is excessively high.Meanwhile poor stability also affects the working performance and service life of fuel cell.
Therefore, it is to reduce fuel cell cost to develop cheap and easy to get, high stability oxygen reduction catalyst, improves its performance and service life
Basic solution route.
Graphene oxide (GO) has the specific surface area of super large, and abundant functional group is contained on surface, such as hydroxyl, carboxyl, ring
Oxygroup etc. has good hydrophily.Therefore, increasingly obtain researcher's by the composite material of template of graphene oxide
Concern.
As a kind of emerging carbon nanomaterial, N doping carbon dots (N-Cdots) and graphene quantum dot (N-GQDs) quilt
Think that there are good potentiality in terms of the non-metallic catalyst of oxygen reduction reaction.Gao etc. utilizes hydro-thermal method, is original with willow leaf
Material, prepare N doping carbon dots, Electrochemical results shows, the material to ORR have very efficient catalytic performance and surely
It is qualitative, and to CH3OH and CO has very strong tolerance (Gao S Y, et al.A green one-arrow-two-hawks
strategy fornitrogen-doped carbon dots as fluorescentink and oxygen reduction
electrocatalysts[J].J.Mater.Chem.A,2014,2:6320-6325.)。
Carbon quantum dot of the doping rich in nitrogen in the carbon skeleton of graphene oxide, may adjust its electronics performance and open up
Wide energy gap causes surface of graphene oxide to generate more " active sites ", and the two synergistic effect is further increased to hydrogen reduction
The electrocatalysis characteristic of reaction.
Invention content
The object of the present invention is to provide a kind of preparation sides of N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst
Method.Preparation method of the present invention is simple, of low cost, environmentally protective, prepared N-Cdots/GO show in alkaline medium and
To the stabilization electrocatalysis characteristic of oxygen reduction reaction in methanol environment.
Technical scheme is as follows：
A kind of preparation method of N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst, using urea as nitrogen source, lemon
Acid is carbon source, graphene oxide is template, is synthesized, is as follows by hydro-thermal method：
By citric acid, urea and graphene oxide (GO) ultrasonic dissolution in ultra-pure water, in 160~200 after being uniformly dispersed
10~13h of hydro-thermal reaction at DEG C, after reaction cooled to room temperature.Through being centrifuged off excessive citric acid, urea, in 40~
It is dried in vacuo 23~25h at 60 DEG C and removes water to get to N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst, wherein
The mass ratio of citric acid, urea and graphene oxide is 54:18:1.
Preferably, the hydrothermal temperature is 180 DEG C, reaction time 12h.
Preferably, the centrifugal rotational speed is 10000rmp, centrifugation time 10min.
Preferably, the vacuum drying temperature is 50 DEG C, and drying time is for 24 hours.
Compared with prior art, the present invention has following remarkable result：
(1) using urea as nitrogen source, nitrogen content is high, green economy, and source is wide.
(2) using citric acid as carbon source, carboxyl is more, is easy to be combined with amino, be captured by urea, and the product prepared is water-soluble
Property is good.
(3) N-Cdots/GO of the invention shows preferable electric conductivity, the capacitance current of superelevation and very strong oxygen also
Former electrocatalysis characteristic, close to commercialization Pt/C electrodes.
(4) compared with being commercialized Pt/C electrodes, N-Cdots/GO of the invention has in alkaline medium preferably to be stablized
Property and methanol tolerance.
Description of the drawings
Fig. 1 is the composition principle figure of N doping carbon dots/graphene oxide (N-Cdots/GO) nano combined elctro-catalyst.
Fig. 2 is (A) GO, (B) N-Cdots, and TEM the and HR-TEM photos of (C~F) N-Cdots/GO nano-complexes.
Fig. 3 is (A) naked GCE, (B) N-Cdots, (C) GO, (D) N-Cdots/GO mixtures, N-Cdots/GO nanometers of (E)
Compound, and cyclic voltammetry curve of (F) the Pt/C electrodes in the 0.1M KOH solutions that nitrogen or oxygen are saturated, sweep fast 10mV
s-1。
Fig. 4 is that (A) chronoamperometry measures Pt/C and N-Cdots/GO nano-complexes in constant potential -0.40V in oxygen
Stability in the 0.1M KOH solutions of gas saturation；(B) chronoamperometry measures Pt/C and N-Cdots/GO nano-complexes and exists
3M CH3Tolerance in OH；(C) the methanol tolerance cyclic voltammetry curve of N-Cdots/GO nano-complexes and (D) Pt/C,
Sweep fast 10mV s-1。
Fig. 5 be (A) each modified electrode and Pt/C electrodes in the 0.1M KOH solutions that oxygen is saturated when 1000rpm rotating speeds
Linear sweep voltammetry (LSV) curve, sweep fast 5mV s-1；(B) N-Cdots/GO nanometers under different rotating speeds (100~1000rpm)
LSV curve of the compound in the 0.1M KOH solutions that oxygen is saturated sweeps fast 5mV s-1；(C) different potentials (- 0.30~-
The K-L curves of N-Cdots/GO nano-complexes under 0.70V), sweep fast 5mV s-1；(D) each modified electrode and Pt/C electrodes be not
Electron transfer number under same current potential (- 0.30~-0.70V)；(E) each modified electrode and Pt/C electrodes are in different potentials (- 0.30
~-0.70V) under kinetic limiting current (jk) curve；(F) N-Cdots/GO nano-complexes and Pt/C electrodes are full in oxygen
Tafel curves in the 0.1M KOH solutions of sum.
Specific implementation mode
The content to facilitate the understanding of the present invention is made the present invention with reference to embodiment and attached drawing further detailed
It describes in detail bright.
Embodiment 1
A kind of system of N doping carbon dots/graphene oxide (N-Cdots/GO) the nano combined elctro-catalyst for preparing the present invention
Preparation Method, such as Fig. 1, include the following steps：
Step 1 weighs 2.673g citric acids, 0.90g urea and 0.05g graphene oxides, and it is super to be dissolved in 30.0mL successively
In pure water, it is put into ultrasound in Ultrasound Instrument, until being uniformly dispersed；
Above-mentioned mixed liquor is transferred in the stainless steel autoclave that 50mL polytetrafluoroethylene (PTFE) is liner by step 2, is placed in
In blowing-type heated oven, the hydro-thermal reaction 12h at 180 DEG C；
Step 3, after reaction, cooled to room temperature, gained dark brown liquid；
Step 4 centrifuges 10min to remove the impurity such as excessive citric acid with supercentrifuge under 10000rmp rotating speeds；
Sample after step 5, centrifugation is placed in 50 DEG C of vacuum drying chambers removes solvent for 24 hours, obtains solid powder, as institute
State N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst.
Embodiment 2
A kind of preparation side of the N doping carbon dots (N-Cdots) prepared for being compared with N-Cdots/GO of the present invention
Method, embodiment 2 are not both that graphene oxide is not used during synthesis as template with the unique of embodiment 1.
Embodiment 3
A kind of preparation preparing the N doping carbon dots/graphene oxide mixture compared with N-Cdots/GO of the present invention
Method is by being directly mixed to get N doping carbon dots made from suitable embodiment 2 with graphene oxide.
Embodiment 4
The N-Cdots of N-Cdots/GO nano-complexes, the preparation of embodiment 2 prepared by embodiment 1, the preparation of embodiment 3
N-Cdots/GO mixtures and template GO carry out morphology characterization analysis, be as follows：
The pattern of each sample uses Tecnai G2 F30 S-Twin high power transmission electron microscopes (HR- with size observation test
TEM, the U.S., FEI Co.), operating voltage 300kV.Before doing Electronic Speculum, it is ultra-thin that the sample of 10 μ L is first added drop-wise to 200 purposes
Carbon is supported on film copper mesh, is placed in and is evaporated aqueous solvent at room temperature, you can Electronic Speculum operation is carried out, as a result referring to Fig. 2.It can by Fig. 2 (A)
Know, prepared GO is in the irregular laminated structure of two dimension, and surface is smooth, and Size Distribution is between tens nanometers to several microns.By
Fig. 2 (B) is it is found that N-Cdots is in unifonn spherical structure, and high monodisperse, morphology and size is more uniform, and grain size is about 5nm.Fig. 2
(C) it is found that it is different from the smooth irregular flake graphite alkene nano material of two-dimensional surface, N-Cdots/GO nano-complexes
Two-dimentional irregular schistose surface uniformly dispersing thickly dotted light grey spot, these spots and prepared N-Cdots shapes
Looks are identical, show that the carbon quantum dot rich in nitrogen is embedded on graphene.It is shone by the HR-TEM of N-Cdots/GO nanocomposites
Piece Fig. 2 (D) and 2 (E) is it is found that preferable crystal form is presented in N-Cdots, and grain size is about 5nm, in graphene film edge fold position
Place, graphene number of plies information can be accurately obtained by light and dark striped.It can be clearly observed rich in nitrogen from Fig. 2 (F)
Carbon quantum dot lattice fringe, adjacent crystal planes spacing is 0.21nm, is corresponded to brilliant in the face of (100) crystal face in graphite-structure
Compartment is away from showing the prepared carbon quantum dot rich in nitrogen with preferable graphite crystalline structure.
Embodiment 5
To the N-Cdots of naked GCE, GO, the preparation of embodiment 2, the N-Cdots/GO mixtures of the preparation of embodiment 3, embodiment 1
The N-Cdots/GO nano-complexes and commercialization Pt/C electrodes of preparation carry out electro-chemical test.
In the present invention, using Ag/AgCl (3mol/L KCl) electrodes of saturation as reference electrode, platinum filament is used as to electrode,
The glass-carbon electrode (GCE) for modifying target substance is used as working electrode, be saturated nitrogen or oxygen potassium hydroxide solution (KOH,
0.1mol/L) it is electrolyte, electrochemistry survey is carried out by electrochemical workstation CHI 660D (Shanghai Chen Hua Instrument Ltd.)
Examination.The preparation of working electrode：By glass-carbon electrode successively in 0.5 μm and 0.05 μm of Al2O3Polishing is in minute surface under polishing powder, in going
Dry bare glassy carbon electrode after being cleaned by ultrasonic in ionized water；Weigh that 2.5mg samples are dissolved in 400 μ L absolute ethyl alcohols and the mixing of water is molten
(V in liquidEthyl alcohol/VWater=1:1) it is uniform that 100 μ L perfluorinated sulfonic acids-polytetrafluoroethylsolution solution (Nafion, 5%) ultrasonic disperse, is added, takes
In 20 μ L mixed solution drop coatings to glass-carbon electrode, drying at room temperature obtains working electrode.
In the present invention, the electronics transfer of oxygen reduction reaction occurs for the catalytic fuel cell for evaluating elctro-catalyst performance
Number, is determined by the following procedure：
Electron transfer number is calculated by Koutechy-Levich (K-L) equation, and formula is as follows：
Wherein, j is current density, jLFor limiting current density, jKFor dynamics current density, ω is electrode rotation rate
(rpm), B is Levich slopes, can be calculated by Levich equations, formula is as follows：
B=0.2nF (DO2)2/3v-1/6CO2(equation 2)
Wherein, the electron number that n is shifted by the single oxygen molecule of reduction, F are Faraday constant (96485C mol-1), it is
Diffusion coefficient (1.9 × 10 of the oxygen in 0.1M KOH solutions-5cm2s-1), ν is the dynamic viscosity of 0.1M KOH solutions
(0.01cm2s-1), it is concentration (1.2 × 10 of the oxygen in 0.1M KOH solutions-6molcm-3)。
Specific implementation step is as follows：
(1) cyclic voltammetric is analyzed
N-Cdots/GO nano-complexes test the electrocatalysis characteristic of oxygen reduction reaction by cyclic voltammetry (CV).Institute
The N-Cdots of preparation, GO, N-Cdots/GO mixtures, N-Cdots/GO nano-complexes and commercialization Pt/C electrodes are in nitrogen
Or the cyclic voltammetry curve in the 0.1M KOH solutions of oxygen saturation is as shown in Figure 3.In the 0.1M KOH solutions of nitrogen saturation,
GO (Fig. 3 C curves a), N-Cdots/GO mixture (Fig. 3 D curves a), N-Cdots/GO nano-complex (Fig. 3 E curve a) and quotient
(capacitance current of preferable electric conductivity and superelevation is presented in Fig. 3 F curves a) to industry Pt/C electrodes, and no apparent reduction peak occurs.
In the 0.1M KOH solutions of oxygen saturation, hydrogen reduction spike potential (- 0.391V, Fig. 3 C curve b) and N-Cdots/GO with GO
(- 0.353V, Fig. 3 D curves b) are different, and N-Cdots/GO nano-complexes show very strong for the hydrogen reduction spike potential of mixture
Hydrogen reduction electrocatalysis characteristic (hydrogen reduction spike potential be -0.219V, Fig. 3 E curve b), close to commercialization Pt/C electrodes oxygen also
Parent peak current potential (- 0.124V, Fig. 3 F curves b).Meanwhile the electric conductivity of N-Cdots/GO nano-complexes is compared with N-Cdots and N-
Cdots/GO mixtures have significant improvement, the peak current density (j with N-Cdots/GO mixturesp=0.823mA
cm-2) compare, the peak current density (j of N-Cdots/GO nano-complexesp=1.150mA cm-2) increase 1.4 times.
(2) stability and methanol tolerance
The stability of N-Cdots/GO nano-complexes is tested by chronoamperometry (i-t), as a result as shown in Figure 4 A.
When constant potential -0.40V, N-Cdots/GO nano-complexes electrode reacts electricity after 11h in the 0.1M KOH solutions that oxygen is saturated
Current density only loses about 6% (Fig. 4 A curve b), and be commercialized Pt/C electrodes and lose about 30% (Fig. 4 A curve a) show N-
Cdots/GO nano-complexes are with good stability in alkaline medium.The methanol of N-Cdots/GO nano-complexes is resistant to
Property by chronoamperometry (i-t) test, as a result as shown in Figure 4 B.It is added into 10.0mL 0.1mol/L KOH solutions
After 3.0mol/L methanol, since the oxidation reaction of methanol and platinum causes catalyst poisoning to inactivate, commercialization Pt/C electrode currents are close
Degree reduces about 55% (Fig. 4 B curves a).On the contrary, N-Cdots/GO nano-complexes are influenced little, electrode current by methanol
Density is held essentially constant (Fig. 4 B curves b).The methanol tolerance of N-Cdots/GO nano-complexes also available cycles voltammetry
It evaluates, N-Cdots/GO nano-complexes and commercialization Pt/C electrodes are without (curve a) and containing 3.0mol/L methanol
(the cyclic voltammetry curve result in curve b) is as shown in Fig. 4 C, 4D for the KOH solution of oxygen saturation.It is followed by Fig. 4 C are almost the same
Ring volt-ampere curve a and b is it is found that N-Cdots/GO nano-complex electrodes show relatively stable oxygen reducing ability, electro-catalysis
Activity is not influenced by methanol, i.e., N-Cdots/GO nano-complexes have good methanol tolerance.This with pass through
Chronoamperometry measures consistent to evaluate the methanol tolerance experimental result of N-Cdots/GO nano-complexes.However, with Fig. 4 D
Curve a is compared, and commercialization Pt/C electrodes show a pair of new in the KOH solution of the oxygen saturation containing 3.0mol/L methanol
The redox peaks of methanol, the reduction peak without oxygen disappear that (curve b) shows that the Pt as catalyst can be sent out with methanol
Raw redox reaction and poisoning and deactivation.
(3) electrochemical kinetics performance
Electrochemical kinetics performance is tested by linear sweep voltammetry (LSV), with the Pine rotating circular disks of a diameter of 5mm
Electrode is working electrode.Naked GCE, GO, N-Cdots, N-Cdots/GO mixture, N-Cdots/GO nano-complexes and commercialization
Pt/C electrodes are in the 0.1M KOH solutions that oxygen is saturated, electrode rotating speed 1000rpm, and sweep speed is 5mV s-1LSV curves
As shown in Figure 5A.Compared with naked GCE, GO, N-Cdots and N-Cdots/GO mixture, N-Cdots/GO nano-complexes have
The take-off potential (0.13V) and half wave potential (- 0.152V) of corrigendum are in close proximity to commercialization Pt/C electrodes.In addition, in electricity
The current density (j) of position -0.8V, N-Cdots/GO nano-complexes are 3.42mA cm-2, it is more than GO (j=1.51mA cm-2),
N-Cdots (j=1.82mA cm-2), N-Cdots/GO mixtures (j=2.55mA cm-2), it is in close proximity to commercialization Pt/C
Electrode (j=4.08mA cm-2), illustrate that N-Cdots/GO nano-complexes have better ORR performances.
Oxygen saturation 0.1M KOH solutions in, N-Cdots/GO nano-complexes electrode different rotating speeds (100~
Linear sweep voltammetry (LSV) curve under 1000rpm) is as shown in Figure 5 B.It is seen that N-Cdots/GO nano-complexes
Current density constantly increase with the increase of electrode rotating speed, this is because with the gradual increase of RDE electrode rotating speeds, electrolysis
The diffusion of liquid is gradually reinforced.In the 0.1M KOH solutions of oxygen saturation, N-Cdots/GO nano-complex electrodes are not
K-L curves under same current potential (- 0.30~-0.70V) are as shown in Figure 5 C.It is seen that K-L curves be straight line, j with
ω-1/2In a linear relationship, therefore, N-Cdots/GO nano-complexes are catalyzed the dissolved oxygen in KOH solution and reduction reaction category occur
In dynamics first order reaction.
N-Cdots, N-Cdots/GO mixture, N-Cdots/GO nano-complexes and Pt/C electrodes different potentials (-
0.30~-0.70V) under ORR reaction process in transfer electron number (n) gone out by K-L slope of a curves and K-L equation calculations,
As a result as shown in Figure 5 D.As seen from the figure, the electron transfer number of N-Cdots or N-Cdots/GO mixtures electrode 2.5 to 3.2 it
Between, show that ORR of the N-Cdots or N-Cdots/GO mixtures electrode in 0.1M KOH solutions mainly passes through 2e-Approach carries out；
The average electron transfer number () of N-Cdots/GO nano-complex electrodes is 3.91, shows N-Cdots/GO nano-complex electricity
ORR of the pole in 0.1M KOH solutions mainly passes through 4e-Approach carries out, this passes through 4e with commercialization Pt/C electrodes (=3.96)-On the way
Diameter carries out similar.N-Cdots, N-Cdots/GO mixture, N-Cdots/GO nano-complexes and commercialization Pt/C electrodes be not
ORR dynamics current densities (j under same current potential (- 0.30~-0.70V)k) curve is as shown in fig. 5e.It can be seen from the figure that
When current potential is -0.70V, the ORR dynamics current densities (j of N-Cdots/GO nano-complex electrodesk=18.4mA cm-2)
Close to commercialization Pt/C electrodes, it is 2.5 times and 4 times of N-Cdots/GO mixtures electrode and N-Cdots electrodes respectively, shows
N-Cdots/GO nano-complexes have better ORR electrocatalysis characteristics.
Oxygen N-Cdots/GO nano-complex electrode surfaces absorption mechanism by Tafel tracing analysis, as a result such as
Shown in Fig. 5 F.It can be seen from the figure that the speed of entire ORR reactions determines that N-Cdots/GO receives at this time by oxygen diffusion control
Tafel slopes (the 114.5mV dec of rice compound-1) slightly larger than the Tafel slopes (106.6mV of commercialization Pt/C catalyst
dec-1), i.e., the electrocatalysis characteristic of N-Cdots/GO nano-complexes close to commercialization Pt/C catalyst electrocatalysis characteristic.
Claims (4)
1. a kind of preparation method of N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst, which is characterized in that specific steps
It is as follows：
By citric acid, urea and graphene oxide ultrasonic dissolution in ultra-pure water, after being uniformly dispersed under 160 ~ 200 oC water
10 ~ 13 h of thermal response, after reaction cooled to room temperature；Through being centrifuged off excessive citric acid, urea, in 40 ~ 60
It is dried in vacuo 23 ~ 25 h under oC and removes water to get to N doping carbon dots/stannic oxide/graphene nano composite electrocatalyst, wherein
The mass ratio of citric acid, urea and graphene oxide is 54: 18 : 1.
2. preparation method as described in claim 1, which is characterized in that the hydrothermal temperature is 180 oC, when reaction
Between be 12 h.
3. preparation method as described in claim 1, which is characterized in that the centrifugal rotational speed is 10000 rmp, centrifugation time
For 10 min.
4. preparation method as described in claim 1, which is characterized in that the vacuum drying temperature is 50 oC, drying time
For 24 h.
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| CN115487844B (en) * | 2022-08-09 | 2023-11-14 | 广州大学 | Catalytic material N-doped carbon dot/CoFe of high-activity ORR 2 O 4 And method for synthesizing the same |
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