CN108493461B - N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof - Google Patents
N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN108493461B CN108493461B CN201810466348.8A CN201810466348A CN108493461B CN 108493461 B CN108493461 B CN 108493461B CN 201810466348 A CN201810466348 A CN 201810466348A CN 108493461 B CN108493461 B CN 108493461B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- drying
- temperature
- solution
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
A catalyst of Fe and Co bimetallic nanoparticles coated with N-doped porous carbon and a preparation method thereof belong to the field of energy materials and electrochemistry. The catalyst takes glucose as a C source, g-C3N4Being N and C sources and templates, FeCl3·6H2O and Co (NO)3)2·6H2And O is a metal source, and the Fe-Co @ NC catalyst with Fe and Co coated by N-doped porous carbon is prepared by adopting a high-temperature step-by-step calcination method, and is of a three-dimensional porous disordered stacking structure. Fe. Co being Fe0.3Co0.7、Fe2O3And the Co phase exists and is uniformly coated in the N-doped porous carbon. Compared with the common Pt-based catalyst, the ORR performance of the catalyst in an alkaline medium is not much different from that of the commercial Pt/C catalyst, the OER performance of the catalyst is far higher than that of the Pt/C catalyst, and the catalyst has higher stability and methanol resistance. Compared with the common bimetallic alloy catalyst, the catalyst has more active species and larger specific surface area. In addition, the catalyst has the advantages of low price and rich sources of raw materials, simple preparation process, contribution to large-scale production and higher practical value.
Description
Technical Field
The invention belongs to the field of energy materials and electrochemistry, and relates to an electrocatalyst for oxygen reduction reaction and oxygen evolution reaction in the fields of fuel cells, electrolyzed water, metal-air batteries and the like and a preparation method thereof.
Background
Fuel cells, metal air cells, electrolyzed water, and the like have become hot spots for research in the field of new energy because of convenience, no pollution, reliable performance, and high energy density. However, the Oxygen electrode reaction (here, specifically, Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER)) of these devices has slow kinetics and high overpotential, and thus greatly hinders the commercialization process thereof. The key to solving this problem is to develop efficient, low cost ORR and OER catalysts to improve their operating efficiency. At present, Pt-based catalysts and Ru/Ir-based catalysts are the catalysts with the best performance for catalyzing ORR and OER respectively, but cannot be used as ORR and OER double-effect catalysts, and the reserves of noble metals Pt, Ru and Ir are limited, the price is high, the stability is poor, and the large-scale application of the noble metals is also limited. Therefore, the development of the bifunctional oxygen electrode catalyst with high catalytic activity, high stability and low cost has important scientific value and practical significance.
The transition metal-nitrogen-carbon catalyst is concerned by the advantages of high ORR activity, stable performance, low price and the like, but the prior single metal doped catalyst is difficult to have excellent dual catalytic functions of ORR and OER. Bimetallic and even multi-metal doped catalysts may theoretically provide a variety of active sites, possibly meeting the requirements of catalyzing ORR and OER processes simultaneously and being used as a dual-effect oxygen electrode catalyst. Literature [ Nano Research 2017,10,2332-]With C3N4As carbon and nitrogen sources, Fe (acac)3And Co (acac)2Fe source and Co source, respectively, and the FeCo alloy loaded FeCo/NC catalyst of the N-doped graphene sheet is prepared by a pyrolysis method after ball milling and mixing. Experimental results show that although the preparation method of the catalyst is simple, the specific surface area is large, the stability is good, the active substance is single, and the catalytic performance of ORR and OER is required to be further improved. Literature [ Journal of Colloid and Interface Science 2018,514,656-]Using melamine as carbon-nitrogen source, FeCl3·6H2O and CoCl2·6H2O is a metal source, and the catalyst (CoFe @ NCNTs) with CoFe alloy particles partially coated in the N-doped carbon nano tube is successfully prepared by adopting a one-step pyrolysis method. The tubular structure of the catalyst is not only beneficial to increasing the active sites of the catalyst, but also beneficial to the mass transfer, and in addition, the tubular structure of the catalyst has excellent stability. However, the ORR and OER properties are inferior, and further improvement is still required.
In summary, although the bimetal doped catalyst has better ORR and OER stability, the activity thereof still cannot meet the requirement of practical application. The reason for this may be that current preparation methods do not allow bimetallic doped catalysts to provide sufficient active site species. The method for doping transition metal step by step has the processes of forming active sites twice or even more, can possibly improve the current situation that the types of the active sites formed by the one-step preparation method are insufficient, and can form various active site configurations so as to improve the ORR and OER performances of the catalyst.
The invention uses cheap FeCl3·6H2O and Co (NO)3)2·6H2O as precursor, glucose as carbon source, g-C3N4The Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles is obtained by a step-by-step pyrolysis method for catalyzing ORR and OER reactions as an C, N source and a pore-forming template.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a catalyst of N-doped porous carbon-coated Fe and Co bimetallic nanoparticles and a preparation method thereof, wherein the catalyst adopts glucose with low price as a C source, and g-C3N4Being N source, C source and template, FeCl3·6H2O and Co (NO)3)2·6H2O is a metal source and is prepared by adopting a high-temperature step-by-step calcination method. Compared with the common Pt-based catalyst, the ORR performance of the catalyst is equivalent to that of the commercial 20 wt.% Pt/C catalyst in an alkaline medium, the OER performance of the catalyst is far higher than that of the commercial 20 wt.% Pt/C catalyst, and the catalyst has higher stability and methanol resistance; in addition, the raw materials are low in price and rich in sources, the preparation process is simple, and the method is favorable forLarge-scale production and high practical value.
In order to achieve the purpose, the invention adopts the technical scheme that:
an N-doped porous carbon-coated Fe-Co @ NC catalyst with Fe and Co bimetallic nanoparticles has a three-dimensional porous structure and a larger specific surface area, and can ensure the mass transfer process of reaction substances in the process of catalyzing ORR and OER; fe. Co being Fe0.3Co0.7、Fe2O3Most of the simple substance Co phase exists in the N-doped porous carbon and is uniformly distributed, the structure can effectively avoid the direct contact of metal particles and electrolyte in the reaction process, and simultaneously inhibit the aggregation of the metal particles and improve the stability of the catalyst; the doping of N atom can produce a certain amount of defect sites and form active species such as pyridine nitrogen, pyrrole nitrogen and metal-N, and the like, and the Fe is coated0.3Co0.7、Fe2O3And the Co particles can activate the N-doped carbon layer, so that the quantity of ORR and OER active sites is greatly increased, and the activity of the catalyst is improved.
A preparation method of an N-doped porous carbon-coated Fe and Co bimetallic nanoparticle Fe-Co @ NC catalyst comprises the following steps:
1) the product obtained by calcining urea at the temperature of 400-600 ℃ for 0.1-24h is named as g-C3N4(ii) a The temperature rising rate from the initial temperature to the calcination temperature is 3-10 ℃ for min-1。
2) Mixing water and ethanol according to the volume ratio of 1:0.01-100 to obtain a solution A, and mixing the product g-C in the step 1)3N4、FeCl3·6H2Dissolving O and glucose in the solution A, heating to 40-100 deg.C, and reacting for 0.1-48 hr to obtain solution B, wherein the concentration of glucose in the solution B is 0.01-1mol L-1. The glucose and FeCl3·6H2The molar ratio of O is 12:1-100, glucose and g-C3N4The mass ratio of (A) to (B) is 10: 0.1-100.
3) Drying the solution B obtained in the step 2) to prepare a catalyst precursor (I).
4) Under the protection of inert gas, inCalcining the catalyst precursor obtained in the step 3) at the temperature of 400 ℃ and 1200 ℃ for 0.1 to 48 hours. The temperature rising rate from the initial temperature to the calcination temperature is 1-10 ℃ for min-1. The inert gas is N2Ar and N2One or more of the mixed gas of/Ar.
5) Mixing water and ethanol at a volume ratio of 1:0.01-100 to obtain solution C, and adding Co (NO)3)2·6H2And O and the product obtained in the step 4) are placed in the solution C for mixing. Said Co (NO)3)2·6H2O and FeCl3·6H2The molar ratio of O is 5: 0.1-100.
6) Drying the solution C obtained in the step 5) to prepare a catalyst precursor II.
7) Calcining the catalyst precursor obtained in the step 6) at the temperature of 400-1200 ℃ for 0.1-48h under the protection of inert gas. The temperature rising rate from the initial temperature to the calcination temperature is 1-10 ℃ for min-1. The inert gas is N2Ar and N2One or more of the mixed gas of/Ar.
Said Co (NO)3)2·6H2O and FeCl3·6H2O can be replaced by any two or more than two of soluble salts of metals such as Mn, Fe, Co, Ni, Cu or Zn.
The drying method in the drying step in the step 3) and the step 6) comprises vacuum oven drying, air oven drying, stirring drying, freeze drying and the like, wherein the drying temperature is-40-500 ℃, and the drying time is 1-100 h.
The Fe-Co @ NC catalyst with the N-doped porous carbon coating Fe and Co bimetallic nanoparticles is used as an ORR and/or OER electrocatalyst of energy storage and conversion devices such as fuel cells, metal-air batteries and electrolyzed water.
The invention has the beneficial effects that:
1) the Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nano-particles prepared by the method utilizes glucose as a C source and g-C3N4Is N source, C source and pore-forming agent, FeCl3·6H2O and Co (NO)3)2·6H2O is a metal source and is prepared by a step-by-step pyrolysis method, the types of active substances can be increased by the step-by-step method, and the simultaneous catalysis of ORR and OER reactions is facilitated.
2) According to the Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nano particles prepared by the method, most of the Fe and Co nano particles are uniformly coated in the N-doped porous carbon, so that the direct contact between metal particles and electrolyte in the reaction process can be effectively avoided, the aggregation of the metal particles is inhibited, and the stability of the catalyst is improved
3) The Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nano-particles prepared by the method of the invention is prepared by regulating and controlling the preparation conditions, such as FeCl3·6H2O and Co (NO)3)2·6H2Molar ratio of O, g-C3N4The controllable preparation of the catalyst can be realized by the mass ratio of the catalyst to glucose, the calcining temperature, the calcining time and the like;
4) the Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles prepared by the method has the advantages of large specific surface area, simple and controllable pore-forming process and capability of ensuring the mass transfer process of reaction species in the ORR and OER processes;
5) the Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles prepared by the method has the advantages of low price of raw materials, wide sources and contribution to realizing commercial development; moreover, the preparation process is simple, economic, safe and good in repeatability, and is beneficial to the amplification production of the catalyst;
6) the Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nano-particles prepared by the method has excellent ORR and OER catalytic performances in an alkaline electrolyte, and the delta E is only 0.84V (the delta E is a bifunctional catalyst performance evaluation parameter, the smaller the delta E is, the better the bifunctional catalytic performance is), which is far smaller than that of a Pt/C catalyst and a single FeCo alloy nano-particle catalyst prepared at present.
7) The Fe-Co @ NC catalyst of the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles prepared by the method has excellent methanol resistance and ORR and OER catalytic stability in an alkaline electrolyte.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample prepared according to example 1.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a sample prepared according to example 1 under a condition of 1 μm.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of a sample prepared according to example 1 at 100 nm.
FIG. 4(a) is a nitrogen adsorption/desorption isotherm curve of a sample prepared according to example 1; FIG. 4(b) is a pore distribution curve of the sample prepared in example 1.
FIG. 5(a) is a plot of samples made according to examples 1-4 versus a comparative example commercial 20 wt.% Pt/C catalyst at O2Saturated 0.1mol L-1ORR polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm.
FIG. 5(b) is a plot of samples made according to examples 1-4 versus a comparative example commercial 20 wt.% Pt/C catalyst at O2Saturated 0.1mol L-1OER polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm.
FIG. 6(a) is a plot of samples made according to examples 1, 5, 6 versus a comparative example commercial 20 wt.% Pt/C catalyst at O2Saturated 0.1mol L-1ORR polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm.
FIG. 6(b) is a plot of samples made according to examples 1, 5, 6 versus a comparative example commercial 20 wt.% Pt/C catalyst at O2Saturated 0.1mol L-1OER polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm.
FIG. 7 is a graph of the sample prepared according to example 1 at O2Saturated 0.1mol L-1Linear Sweep Voltammetry (LSV) curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 400rpm, 900rpm, 1600rpm, 2500 rpm.
FIG. 8 is a Koutecky-Levich (K-L) curve corresponding to the LSV spectrum of FIG. 7.
FIG. 9(a) is a graph of the sample prepared according to example 1 at O2Saturated 0.1mol L-1The ORR polarization curve before and after 8000 circles of accelerated aging test (CV scanning range-0.4-0.1V) in KOH electrolyte at room temperature, the scanning speed: 10mV s-1And the rotating speed: 1600 rpm. FIG. 9(b) is a graph of the sample prepared according to example 1 at O2Saturated 0.1mol L-1OER polarization curve before and after 2000-turn accelerated aging test (CV scanning range 0.4-0.8V) in KOH electrolyte at room temperature, scanning speed: 10mV s-1And the rotating speed: 1600 rpm.
FIG. 10 shows the samples obtained in example 1 at room temperature and O2Saturated 0.1mol L-1KOH electrolyte, O2Saturated 3mol L-1CH3OH+0.1mol L-1CV plot in KOH electrolyte, sweep rate: 10mV s-1。
FIG. 11 is a graph of the comparative example commercial 20 wt.% Pt/C catalyst at room temperature with O2Saturated 0.1mol L-1KOH electrolyte, O2Saturated 3mol L-1CH3OH+0.1mol L-1CV plot in KOH electrolyte, sweep rate: 10mV s-1。
The reference electrodes used in the test of the invention are all KCl saturated Ag/AgCl electrodes.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to these specific examples.
Example 1: G-Fe-Co @ NC-1:1-900-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 1:1 and FeCl is added first3·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 135mg of Co (NO)3)2·6H2Placing the O and the obtained Fe @ NC-900 catalyst in a mixed solution of 10mL of deionized water and 20mL of ethanol, and stirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at the temperature of 80 ℃ for 10 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping at 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 800 ℃ for calcination for 30min, and the target catalyst G-Fe-Co @ NC-1: 1-900-800-one is obtained after natural cooling.
Example 2: G-Fe-Co @ NC-2:1-900-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 2:1, and FeCl is added firstly3·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、250mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 135mg of Co (NO)3)2·6H2O and the obtained Fe @ NC-900 catalyst are put into a mixed solution of 10mL of deionized water and 20mL of ethanol and stirredStirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at the temperature of 80 ℃ for 10 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping at 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 800 ℃ for calcination for 30min, and the target catalyst G-Fe-Co @ NC-2: 1-900-;
example 3: G-Fe-Co @ NC-2:3-900-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 2:3, and FeCl is added firstly3·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 203mg of Co (NO)3)2·6H2Placing the O and the obtained Fe @ NC-900 catalyst in a mixed solution of 10mL of deionized water and 20mL of ethanol, and stirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at the temperature of 80 ℃ for 10 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping at 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 800 ℃ for calcination for 30min, and the target catalyst G-Fe-Co @ NC-2:3-900-800 is obtained after natural cooling;
example 4: G-Fe-Co @ NC-2:4-900-3·6H2O and Co (NO)3)2·6H2Molar mass of OThe amount ratio is 2:4, and FeCl is added firstly3·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; 270mg of Co (NO)3)2·6H2Placing the O and the obtained Fe @ NC-900 catalyst in a mixed solution of 10mL of deionized water and 20mL of ethanol, and stirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at the temperature of 80 ℃ for 10 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping at 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 800 ℃ for calcination for 30min, and the target catalyst G-Fe-Co @ NC-2:4-900-800 is obtained after natural cooling;
example 5: G-Co-Fe @ NC-1:1-900-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 1:1 and Co (NO) is added first3)2·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、135mg Co(NO3)2·6H2O and 500mg of glucose were dissolved in the A solution, which was then put in an oil bathHeating at 80 ℃ for 8h to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying in an air drying oven at 80 ℃ for 10h to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 125mg FeCl3·6H2Placing the O and the obtained Fe @ NC-900 catalyst in a mixed solution of 10mL of deionized water and 20mL of ethanol, and stirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at the temperature of 80 ℃ for 10 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping at 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 800 ℃ for calcination for 30min, and the target catalyst G-Fe-Co @ NC-1: 1-900-800-one is obtained after natural cooling.
Example 6: G-FeCo @ NC-1:1-900-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 1:1 and FeCl is added simultaneously3·6H2O and Co (NO)3)2·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2O、135mg Co(NO3)2·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 5 ℃ for min under the protection of nitrogen-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; placing the calcined powder in quartz boat again, and keeping under nitrogen protection at 5 deg.C for min-1Heating to 800 deg.C by programBurning for 30min, and naturally cooling to obtain the target catalyst G-FeCo @ NC-1: 1-900-.
Example 7: G-Fe @ NC-900(G is glucose, Fe means FeCl in raw material3·6H2O, 900 denotes a first pyrolysis temperature of 900 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, uniformly grinding the catalyst precursor I, putting the ground catalyst precursor into a quartz boat, heating the catalyst precursor to 900 ℃ in a program of 5 ℃ for min-1 under the protection of nitrogen, calcining the catalyst precursor for 1h, and naturally cooling the catalyst precursor to obtain a target catalyst Fe @ NC-900;
example 8: G-Fe-Co @ NC-1:1-600-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 1:1 and FeCl is added first3·6H2O, 600 means the first pyrolysis temperature is 600 ℃, 600 means the second pyrolysis temperature is 600 ℃)
Placing urea in a tube furnace under nitrogen protection at 3 deg.C for 3 min-1The temperature is programmed to 400 ℃ and the mixture is calcined for 1h to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath pan at 60 ℃ for 2 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in a vacuum drying oven at 50 ℃ for 48 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 3 ℃ for min under the protection of nitrogen-1The temperature is programmed to 600 ℃, the calcination is carried out for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 135mg of Co (NO)3)2·6H2O and obtaining Fe @ NCPlacing the catalyst of-900 in a mixed solution of 10mL of deionized water and 20mL of ethanol, and stirring for 2 hours to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at 50 ℃ for 48 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping at 3 ℃ for min under the protection of nitrogen-1The temperature is programmed to 600 ℃ and calcined for 30min, and the target catalyst G-Fe-Co @ NC-1: 1-600-one is obtained after natural cooling.
Example 9: G-Fe-Co @ NC-1:1-1100-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 1:1 and FeCl is added first3·6H2O, 1100 denotes a first pyrolysis temperature of 1100 ℃ and 1100 denotes a second pyrolysis temperature of 1100 ℃)
Placing urea in a tube furnace under nitrogen protection at 10 deg.C for 10 min-1The temperature is programmed to 600 ℃ and the mixture is calcined for 6 hours to obtain g-C3N4(ii) a Mixing 20ml water and 10ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath pan at 100 ℃ for 12 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 300 ℃ for 3 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping the temperature for 10 min under the protection of nitrogen-1The temperature is programmed to 1100 ℃ and calcined for 6h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 135mg of Co (NO)3)2·6H2Placing the O and the obtained Fe @ NC-900 catalyst in a mixed solution of 10mL of deionized water and 20mL of ethanol, and stirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying for 3 hours in an air drying oven at 300 ℃ to obtain a catalyst precursor II; placing the precursor II in a mortar, grinding uniformly, placing in a quartz boat, and keeping the temperature for 10 min under the protection of nitrogen-1The temperature is programmed to 1100 ℃ for calcination for 6h, and the target catalyst G-Fe-Co @ NC-1:1-1100 is obtained after natural cooling.
Example 10: G-Fe-Co @ NC-1:1-900-3·6H2O and Co (NO)3)2·6H2The molar mass ratio of O is 1:1 and FeCl is added first3·6H2O, 900 means the first pyrolysis temperature is 900 ℃, 800 means the second pyrolysis temperature is 800 ℃)
Placing urea in a tube furnace under nitrogen protection at 5 deg.C for 5 min-1The temperature is programmed to 550 ℃ and the mixture is calcined for 4 hours to obtain g-C3N4(ii) a Mixing 20ml water and 50ml ethanol to obtain solution A, and collecting 100mg g-C3N4、125mg FeCl3·6H2Dissolving O and 500mg of glucose in the solution A, heating the solution A in an oil bath kettle at 80 ℃ for 8 hours to obtain a solution B, transferring the uniformly mixed solution B into a culture dish, and drying the solution B in an air drying oven at 80 ℃ for 10 hours to obtain a catalyst precursor I. Putting the catalyst precursor I into a mortar, grinding uniformly, putting into a quartz boat, and keeping at 5 ℃ for min under the protection of argon-1The temperature is programmed to 900 ℃ and calcined for 1h, and the Fe @ NC-900 catalyst is obtained after natural cooling; then 135mg of Co (NO)3)2·6H2Placing the O and the obtained Fe @ NC-900 catalyst in a mixed solution of 10mL of deionized water and 50mL of ethanol, and stirring for 2h to obtain a solution C; transferring the uniformly mixed solution C into a culture dish, and drying the solution C in an air drying oven at the temperature of 80 ℃ for 10 hours to obtain a catalyst precursor II; placing the precursor II in a mortar, uniformly grinding, placing in a quartz boat, and keeping at 5 ℃ for min under the protection of argon-1The temperature is programmed to 800 ℃ for calcination for 30min, and the target catalyst G-Fe-Co @ NC-1: 1-900-800-one is obtained after natural cooling.
Comparative example 1: commercial 20 wt.% Pt/C catalyst (Alfa Aesar)).
FIG. 1 is an X-ray diffraction (XRD) pattern of a sample prepared according to example 1. JCPDS card analysis of the XRD spectrum shows that the metal species in the sample of example 1 contains three crystal structures: the two characteristic peaks appearing at 45.0 and 65.7 degrees are ascribed to Fe0.3Co0.7(JCPDS 48-1818) at 44.2o, 51.5o、75.9oThe characteristic peak of Co nanoparticles (JCPDS89-7093) appears at 29.8o、47.6o、52.0oPeaks appearing ascribed to Fe2O3And (3) nanoparticles. Furthermore, at 26.5oA peak near toBelongs to the (002) surface (JCPDS 20-0258) of graphite carbon; the carbon material has a good graphitized structure.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a sample prepared according to example 1. It can be seen from fig. 2 that a large number of metal particles in the sample prepared in example 1 are coated in the carbon shell and uniformly distributed on the three-dimensional porous carbon with disordered stacking, and besides, a small number of bare nanoparticles are distributed on the surface of the catalyst. The disordered stacking carbon structure can effectively improve the porosity, the specific surface area and the like of the catalyst.
FIG. 3 is a Transmission Electron Microscope (TEM) photograph of a sample prepared according to example 1. As can be seen more clearly in fig. 3, the sample prepared in example 1 has a large number of metal particles coated in the carbon shell and uniformly distributed on the porous carbon, the size of the metal particles being about 20-50 nm. The coating structure can avoid the direct contact of metal particles and electrolyte solution, and improve the stability of the material.
Fig. 4(a) is a nitrogen adsorption/desorption isotherm curve of a sample prepared according to example 1. It can be seen from the graph that the sample obtained in example 1 is in P/P0Shows a hysteresis loop (IV type adsorption curve) within the range of 0.4-1, indicates that a mesoporous structure exists, and the calculation shows that the specific surface area of the catalyst is as high as 403m2g-1. FIG. 4(b) shows the pore size distribution of the sample prepared in example 1 at 3.5 nm. The larger specific surface area and rich pore structure facilitate mass transfer and expose more active sites, thereby improving ORR and OER performance.
FIG. 5(a) is a graph of samples prepared according to examples 1-4 and comparative example 1 at O2Saturated 0.1mol L-1ORR polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm. FIG. 5(b) is a graph of samples prepared according to examples 1-4 and comparative example 1 at O2Saturated 0.1mol L-1OER polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm. As can be seen from fig. 5(a) and 5(b), the ratio of the two metal atoms has a large influence on the electrochemical performance of the catalyst. The atomic ratio of Fe and Co is 2:1, and the ORR initial potential is the best; the atomic ratio of Fe to Co is 1:1, and the OER performance is the best. From ORR and OER dual function angleConsidering that the atomic ratio of Fe and Co is 1:1, the minimum Delta E is 0.84V, and ORR and OER performance is optimal (generally, OER is 10mA cm at j)-2And ORR at j ═ 3.0mA cm-2The potential difference delta E between the two is used for measuring the bifunctional electrocatalytic performance of the electrocatalyst, and the smaller the delta E is, the better the bifunctional electrocatalytic performance is).
FIG. 6(a) is a graph of samples prepared according to examples 1, 5, 6 and 7 and comparative example 1 at O2Saturated 0.1mol L-1ORR polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm. FIG. 6(b) is a graph of the samples prepared according to examples 1, 5, 6 and 7 and comparative example 1 at O2Saturated 0.1mol L-1OER polarization curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 1600 rpm. The ORR performance of the sample prepared according to example 1 was better than that of the sample prepared according to example 5 and that of the sample prepared according to example 6, but slightly lower than that of the sample prepared according to example 7, indicating that the samples prepared according to examples 1 and 7 exhibited superior ORR activity. E of the sample prepared in example 1, compared to commercial Pt/C1/2It is only 10mV lower than Pt/C, which indicates that the sample prepared in example 1 is a good prospect ORR catalyst. Further, from the OER curve shown in FIG. 6(b), it can be seen that the OER performance of the sample prepared in example 1 is the best. It can be seen by calculating Δ E that the sample made in example 1 (Δ E ═ 0.84V) is the most superior bifunctional catalyst.
FIG. 7 is a graph of the sample prepared according to example 1 at O2Saturated 0.1mol L-1Linear Sweep Voltammetry (LSV) curve at room temperature in KOH electrolyte, sweep rate: 10mV s-1And the rotating speed: 400rpm, 900rpm, 1600rpm, 2500 rpm. As can be seen from fig. 7, the ORR initial potential of the sample prepared in example 1 remained constant with increasing electrode rotation speed, but the limiting diffusion current density increased.
FIG. 8 is a Koutecky-Levich (K-L) curve obtained from the LSV curve (FIG. 9) of the sample prepared according to example 1. The electron transfer number of the surface-catalyzed ORR of example 1 was calculated to be 4.08 according to the K-L equation, indicating that the sample prepared in example 1 catalyzes ORR by participating in the reaction with 4 electron process.
FIG. 9(a) is a graph of the sample prepared according to example 1 at O2Saturated 0.1moL L-1Comparing ORR polarization curves after 8000 circles of accelerated aging tests (CV scanning range-0.4-0.1V) in KOH electrolyte, and scanning speed: 10mV s-1And the rotating speed: 1600 rpm; FIG. 9(b) is sample O obtained in example 12Saturated 0.1moL L-1OER curve comparison graph after 2000 circles of accelerated aging tests (CV scanning range of 0.4-0.8V) are carried out in KOH electrolyte, and scanning speed is as follows: 10mV s-1And the rotating speed: 1600 rpm. As can be seen from fig. 9(a), the CV curve of the catalyst prepared in example 1 was not significantly changed after 8000 cycles, indicating that the catalyst prepared in example 1 has better ORR stability. As can be seen from FIG. 9(b), the OER curve of the catalyst obtained in example 1 was 10mA cm after 2000 cycles-2The corresponding potential was shifted only 5mV positively, indicating that the catalyst prepared in example 1 also had significant stability during OER.
FIG. 10 shows the results of the samples obtained in example 1 under N2Saturation and O2Saturated 0.1M KOH solution and O2Saturated 0.1M KOH +3M CH3CV curve in OH solution, sweep rate: 10mV s-1. As can be seen from FIG. 10, the catalyst prepared in example 1 was prepared by adding 3M CH to the electrolyte3The CV curves of the Fe-Co @ NC catalyst before and after OH did not change significantly, indicating that the catalyst prepared in example 1 is less affected by methanol fuel and can be used as a cathode catalyst for a methanol fuel cell.
FIG. 11 shows comparative example 1 in which N is2Saturation and O2Saturated 0.1M KOH solution and O2Saturated 0.1M KOH +3M CH3CV curve in OH solution, sweep rate: 10mV s-1. As can be seen in FIG. 11, the commercial 20 wt.% Pt/C catalyst was added with 3M CH3The apparent methanol oxidation peak detected in the potential range of-0.5 to 0.2V after OH indicates poor methanol resistance of comparative example 1.
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.
Claims (9)
1. A preparation method of an N-doped porous carbon-coated Fe and Co bimetallic nanoparticle Fe-Co @ NC catalyst is characterized in that the catalyst adopts glucose as a C source and g-C3N4Being N source, C source and template, FeCl3·6H2O and Co (NO)3)2·6H2O is a metal source and is prepared by adopting a high-temperature step-by-step calcination method; the catalyst is in a three-dimensional porous structure, so that the mass transfer process of the reaction species can be ensured; fe. Co being Fe0.3Co0.7、Fe2O3The simple substance Co phase exists, is coated in the N-doped porous carbon and is uniformly distributed, so that various active species can be provided, and the activity of the catalyst is improved; meanwhile, the catalyst structure can effectively avoid the direct contact of the metal particles and the electrolyte in the reaction process, inhibit the aggregation of the metal particles and improve the stability of the catalyst;
the preparation method specifically comprises the following steps:
1) the product obtained by calcining urea at the calcining temperature of 400-600 ℃ for 0.1-24h is named as g-C3N4；
2) Mixing water and ethanol to obtain solution A, and mixing the product g-C obtained in the step 1)3N4、FeCl3·6H2Dissolving O and glucose in the solution A, heating to 40-100 deg.C, and reacting for 0.1-48h to obtain solution B, wherein the concentration of glucose in the solution B is 0.01-1mol L-1(ii) a The glucose and FeCl3·6H2The molar ratio of O is 12:1-100, glucose and g-C3N4The mass ratio of (A) to (B) is 10: 0.1-100;
3) drying the solution B obtained in the step 2) to prepare a catalyst precursor I;
4) calcining the catalyst precursor (I) obtained in the step 3) under the protection of inert gas;
5) mixing water and ethanol to obtain solution C, and adding Co (NO)3)2·6H2O and the product obtained in the step 4) are placed in the solution C to be mixed; said Co (NO)3)2·6H2O and FeCl3·6H2The molar ratio of O is 5: 0.1-100;
6) drying the solution C obtained in the step 5) to prepare a catalyst precursor II;
7) calcining the catalyst precursor obtained in the step 6) under the protection of inert gas to obtain the Fe-Co @ NC catalyst.
2. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as claimed in claim 1, wherein the Co (NO) is used as a catalyst3)2·6H2O and FeCl3·6H2O can be replaced by any two or more of soluble salts of Mn, Fe, Co, Ni, Cu or Zn metals.
3. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as claimed in claim 1 or 2, wherein the calcination temperature in the steps 4) and 7) is 400-1200 ℃, and the calcination time is 0.1-48 h.
4. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as the claims 1 or 2, wherein the volume ratio of water to ethanol in the step 2) is 1: 0.01-100; the volume ratio of the water to the ethanol in the step 5) is 1: 0.01-100.
5. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as claimed in claim 3, wherein the volume ratio of the water to the ethanol in the step 2) is 1: 0.01-100; the volume ratio of the water to the ethanol in the step 5) is 1: 0.01-100.
6. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as claimed in claim 1, 2 or 5, wherein the drying method in the drying steps in the steps 3) and 6) is one or more of vacuum oven drying, air oven drying, stirring drying and low-temperature freeze drying, wherein the drying temperature is-40-500 ℃, and the drying time is 1-100 h.
7. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as claimed in claim 4, wherein the drying method in the drying steps in the steps 3) and 6) is one or more of vacuum oven drying, air oven drying, stirring drying and low-temperature freeze drying, the drying temperature is-40-500 ℃, and the drying time is 1-100 h.
8. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as the claims 1, 2, 5 or 7, wherein the heating rate of the initial temperature to the calcination temperature in the steps 1), 4) and 7) is 1-10 ℃ for min-1。
9. The preparation method of the Fe-Co @ NC catalyst with the N-doped porous carbon-coated Fe and Co bimetallic nanoparticles as claimed in claim 6, wherein the heating rate of the temperature rising from the room temperature to the calcination temperature in the steps 1), 4) and 7) is 1-10 ℃ for min-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810466348.8A CN108493461B (en) | 2018-05-08 | 2018-05-08 | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810466348.8A CN108493461B (en) | 2018-05-08 | 2018-05-08 | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108493461A CN108493461A (en) | 2018-09-04 |
| CN108493461B true CN108493461B (en) | 2021-01-19 |
Family
ID=63353169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810466348.8A Expired - Fee Related CN108493461B (en) | 2018-05-08 | 2018-05-08 | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108493461B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012733B (en) * | 2018-09-06 | 2020-07-24 | 东北大学 | g-C3N4Preparation method of core-shell structure nano composite coated with metal |
| CN109680299B (en) * | 2019-01-22 | 2020-05-22 | 浙江大学 | Three-dimensional self-supporting gamma-Fe2O3-NC/CF electrode and preparation method and application thereof |
| CN110120526B (en) * | 2019-03-20 | 2022-01-11 | 江苏大学 | Preparation method and application of transition metal alloy/multi-dimensional carbon-based composite electrode material |
| CN110071299A (en) * | 2019-04-28 | 2019-07-30 | 三峡大学 | Dilval/nitrogen-doped carbon elctro-catalyst preparation and in the application that can be filled in zinc and air cell |
| CN110176606A (en) * | 2019-05-21 | 2019-08-27 | 大连理工大学 | A kind of Co@NC high dispersive catalyst with core-casing structure, preparation method and applications |
| CN110354884A (en) * | 2019-06-27 | 2019-10-22 | 华南师范大学 | A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application |
| CN110280288B (en) * | 2019-07-04 | 2021-12-17 | 山西师范大学 | Preparation method of transition metal-nitrogen co-doped carbon material oxygen reduction/oxygen precipitation bifunctional catalyst |
| CN110429290A (en) * | 2019-08-06 | 2019-11-08 | 四川轻化工大学 | A method of preparing nitrogen-doped carbon material load transition metal compound catalyst |
| CN110860303B (en) * | 2019-11-21 | 2022-08-09 | 青岛科技大学 | Preparation method and application of metal and metal carbide reinforced transition metal-nitrogen active site carbon-based electrocatalyst |
| CN111437858A (en) * | 2020-03-10 | 2020-07-24 | 上海电力大学 | N/O double-doped metal carbon-coated carbide nanoparticle composite material and preparation method thereof |
| CN111531181B (en) * | 2020-05-11 | 2022-12-16 | 中国科学院重庆绿色智能技术研究院 | Preparation method of high-performance porous honeycomb tin-carbon lithium battery cathode material |
| CN111554945A (en) * | 2020-05-27 | 2020-08-18 | 青岛科技大学 | High-efficiency carbon-based electrocatalyst and preparation method and application thereof |
| CN112007677A (en) * | 2020-07-24 | 2020-12-01 | 同济大学 | Nitrogen-doped iron nanotube, and preparation method and application thereof |
| CN112490451A (en) * | 2020-11-05 | 2021-03-12 | 上海电力大学 | Cu-CoNCNs catalyst derived from folic acid, preparation and application thereof |
| CN113122865B (en) * | 2021-03-09 | 2022-02-11 | 中国科学院大连化学物理研究所 | Multi-carbon hybridized NiFe-based efficient alkaline water oxidation catalyst |
| CN113333007B (en) * | 2021-04-28 | 2023-02-24 | 暨南大学 | Nitrogen-doped cobalt iron/carbon catalyst capable of efficiently activating persulfate and preparation method and application thereof |
| CN113368883A (en) * | 2021-06-08 | 2021-09-10 | 新乡医学院 | 0D/3D Fe2O3 QDs/g-C3N4Preparation method of hybrid photo-Fenton catalyst |
| CN113394413B (en) * | 2021-06-16 | 2022-06-03 | 福州大学 | Preparation method of catalyst for cathode oxygen reduction reaction based on two-dimensional graphite phase carbon nitride cobalt doped porous carbon material |
| CN113594479A (en) * | 2021-07-05 | 2021-11-02 | 河南师范大学 | Preparation method of Fe and N co-doped porous carbon zinc air battery catalyst |
| CN114094125B (en) * | 2021-10-13 | 2022-11-18 | 江苏大学 | CoFe/CeO 2 Preparation method and application of-nitrogen-doped carbon nanotube composite electrode catalyst material |
| CN114433156B (en) * | 2022-01-20 | 2024-01-09 | 大连海事大学 | Fe/Fe with 3D structure 3 C@FeNC difunctional oxygen electrocatalyst and preparation method and application thereof |
| CN115954491B (en) * | 2022-12-01 | 2023-10-27 | 中南大学 | Preparation method of nitrogen-doped functionalized carbon-supported platinum transition metal binary ordered alloy catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517523A (en) * | 2011-12-15 | 2012-06-27 | 北京科技大学 | Iron-cobalt-based endogenous amorphous composite material |
| CN105826572A (en) * | 2016-05-10 | 2016-08-03 | 大连理工大学 | N and S dual-doped carbon nanotube-coated FexC catalyst and preparation method and application thereof |
| CN107039660A (en) * | 2017-06-07 | 2017-08-11 | 北京化工大学常州先进材料研究院 | The preparation of the porous carbon microsphere of Fe NPS codopes and its it is used as the application of ORR catalyst |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106898786B (en) * | 2015-12-18 | 2019-07-19 | 中国科学院大连化学物理研究所 | A kind of oxygen reduction catalyst and its preparation and application |
| CN106669758A (en) * | 2016-12-26 | 2017-05-17 | 华东理工大学 | Dual-function oxygen electrode catalyst containing non-noble-metal nanoparticles coated with nitrogen-doped porous carbon layer and preparation method of dual-function oxygen electrode catalyst |
| CN107051568B (en) * | 2017-05-08 | 2019-10-22 | 中南大学 | Two cobaltous selenide@N-CT composite catalysts of a kind of analysis oxygen Fe doping and its preparation method and application |
| CN107093749B (en) * | 2017-06-02 | 2019-06-25 | 中南大学 | A kind of bimetallic codope carbon nano-composite material, bimetallic-nitrogen-carbon nanocatalyst and its preparation method and application |
| CN107857249B (en) * | 2017-11-23 | 2020-06-16 | 大连理工大学 | Preparation method of nitrogen-doped annular hollow nano carbon material |
-
2018
- 2018-05-08 CN CN201810466348.8A patent/CN108493461B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517523A (en) * | 2011-12-15 | 2012-06-27 | 北京科技大学 | Iron-cobalt-based endogenous amorphous composite material |
| CN105826572A (en) * | 2016-05-10 | 2016-08-03 | 大连理工大学 | N and S dual-doped carbon nanotube-coated FexC catalyst and preparation method and application thereof |
| CN107039660A (en) * | 2017-06-07 | 2017-08-11 | 北京化工大学常州先进材料研究院 | The preparation of the porous carbon microsphere of Fe NPS codopes and its it is used as the application of ORR catalyst |
Non-Patent Citations (2)
| Title |
|---|
| Enhancement of ORR catalytic activity by multiple heteroatom-doped carbon materials;Dae-wook Kim等;《Phys.Chem.Chem.Phys》;20141009;第17卷(第407期);第407-413页 * |
| 过渡金属/氮掺杂石墨催化剂的制备及电催化氧还原;张蓉等;《分子催化》;20141215(第06期);第553-563页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108493461A (en) | 2018-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108493461B (en) | N-doped porous carbon-coated Fe and Co bimetallic nanoparticle catalyst and preparation method thereof | |
| CN108906106B (en) | FeNi/N-C high-dispersion core-shell structure catalyst and preparation method thereof | |
| CN108543545B (en) | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications | |
| Chen et al. | Rational design of hollow N/Co-doped carbon spheres from bimetal-ZIFs for high-efficiency electrocatalysis | |
| Chen et al. | From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis | |
| Zhang et al. | Spinel CoFe2O4 supported by three dimensional graphene as high-performance bi-functional electrocatalysts for oxygen reduction and evolution reaction | |
| Tang et al. | Cobalt and nitrogen codoped ultrathin porous carbon nanosheets as bifunctional electrocatalysts for oxygen reduction and evolution | |
| Li et al. | Co9S8-porous carbon spheres as bifunctional electrocatalysts with high activity and stability for oxygen reduction and evolution reactions | |
| Li et al. | Incorporation of Fe3C and pyridinic N active sites with a moderate N/C ratio in Fe–N mesoporous carbon materials for enhanced oxygen reduction reaction activity | |
| Fu et al. | Spinel MnCo 2 O 4 nanoparticles cross-linked with two-dimensional porous carbon nanosheets as a high-efficiency oxygen reduction electrocatalyst | |
| Amin et al. | Microwave heated synthesis of carbon supported Pd, Ni and Pd–Ni nanoparticles for methanol oxidation in KOH solution | |
| CN110142058B (en) | F127-induced three-dimensional porous FeNi-NC dual-functional electrocatalyst and preparation method thereof | |
| CN104923204A (en) | Preparation method for graphene-coated metal nanometer particle catalyst and application of graphene-coated metal nanometer particle catalyst | |
| Yang et al. | Metal-organic framework-derived metal-free highly graphitized nitrogen-doped porous carbon with a hierarchical porous structure as an efficient and stable electrocatalyst for oxygen reduction reaction | |
| CN109659570B (en) | Application of metal organic framework compound hollow microspheres loaded with iron cobalt sulfide | |
| CN112221530A (en) | Preparation method and application of non-noble metal single-atom dual-function electrocatalyst | |
| Jeerh et al. | Perovskite oxide LaCr0. 25Fe0. 25Co0. 5O3-δ as an efficient non-noble cathode for direct ammonia fuel cells | |
| CN113549935A (en) | Heteroatom-doped transition metal monoatomic catalyst and preparation method and application thereof | |
| Yu et al. | Facile synthesis of Nafion-supported Pt nanoparticles with ultra-low loading as a high-performance electrocatalyst for hydrogen evolution reaction | |
| Lin et al. | Rapid fabrication of FexNi2− xP4O12 and graphene hybrids as electrocatalyst for highly efficient oxygen evolution reaction | |
| Shang et al. | Effect of Co-Fe alloy nanoparticles on the surface electronic structure of molybdenum disulfide nanosheets and its application as a bifunctional catalyst for rechargeable zinc air battery | |
| Cui et al. | FeNi co-doped electrocatalyst synthesized via binary ligand strategy as a bifunctional catalyst for Zn-air flow battery | |
| Huang et al. | Fe–N–C nanostick derived from 1D Fe-ZIFs for electrocatalytic oxygen reduction | |
| Luong et al. | Unraveling the formation of optimum point in NiCo-based electrocatalysts for urea oxidation reaction | |
| Lian et al. | ZIF-derived porous carbon supported cobalt and selenium dual sites enhanced oxygen reduction reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210119 Termination date: 20210508 |