CN110444772A - A kind of bimetallic base Fe-Co-N-S codope C catalyst and the preparation method and application thereof - Google Patents
A kind of bimetallic base Fe-Co-N-S codope C catalyst and the preparation method and application thereof Download PDFInfo
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- CN110444772A CN110444772A CN201910798802.4A CN201910798802A CN110444772A CN 110444772 A CN110444772 A CN 110444772A CN 201910798802 A CN201910798802 A CN 201910798802A CN 110444772 A CN110444772 A CN 110444772A
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- 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
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Abstract
The invention discloses a kind of preparation methods of bimetallic base Fe-Co-N-S codope C catalyst, it is characterized in that, include the following steps: that 40 mg ZIF-67 1) are added in the container equipped with 20 mL ethyl alcohol, the aqueous solution of 2 mL FeTsPc is rapidly joined after ultrasonic disperse is uniform, the mass ratio for controlling wherein ZIF-67/FeTsPc is 1/0.25-2, centrifugal drying after 24 h of magnetic agitation, obtains FeTsPc/ZIF-67 composite material；2) composite sample that 120 mg step 1) obtain is weighed, is placed in quartz tube furnace under Ar atmosphere in 500-1000 DEG C of 3 h of heat treatment, the i.e. Fe-Co-N-S-C of bimetallic base Fe-Co-N-S codope C catalyst is obtained.This method and process is simple, operating condition is mildly controllable, resulting materials excellent electrochemical performance and low in cost, has a good application prospect.
Description
Technical field
The present invention relates to electro-catalysis and fuel cell field, and in particular to a kind of novel bimetallic base Fe-Co-N-S is total
The preparation and its application in fuel battery negative pole oxygen reduction reaction for adulterating C catalyst, especially a kind of bimetallic base Fe-
Co-N-S codope C catalyst and the preparation method and application thereof.
Background technique
Fuel cell can be applied to various transports and portable electronic as a kind of environmental-friendly and efficient technology
The electrochemical energy conversion equipment of equipment.However, the slow dynamics of Cathodic oxygen reduction, that is, ORR seriously hinders fuel electricity
The development of pool technology.So far, noble metal sill such as Pt, Pd or Ir are considered as most effective ORR elctro-catalyst.However, this
The disadvantages of high cost of class material, raw material are rare and stability is poor significantly limits the large-scale commercial applications application of fuel cell.
Therefore, exploitation has the base metal ORR elctro-catalyst of cost-effectiveness and function admirable most important.
Currently, base metal ORR elctro-catalyst of greatest concern is transient metal doped M-N-C(M=Fe, Co) body
System, by rationally designing and constructing its active bit architecture, it can show the performance to compare favourably with Pt base catalyst.In recent years
The study found that prepare presoma used in M-N-C type catalyst structure and its ORR performance it is closely related.Metal organic frame
MOFs is a kind of novel porous materials being combined by metal and organic ligand, is the ideal for preparing M-N-C type ORR catalyst
Presoma.In order to improve the ORR activity of porous C catalyst derived from metal organic frame MOFs, in metal organic frame MOFs
On the basis of be further introduced into the broad interest that outer secondary hetero atom source has attracted people, introduced outer secondary hetero atom packet
The metal heteroatoms such as the nonmetallic heteroatoms such as N, P and S and Fe, Co are included, relate generally to following several documents: (1) 2019 years
" Applied Catalysis B " reports the Co/Ni/N tri- obtained by the ZIF-67 of three -1,10- phenanthroline nickel of nitric acid doping
C catalyst is adulterated under acid and alkaline condition to the performance study of oxygen reduction reaction；(2) 2019 years " ACS
Sustainable Chemistry Engineering " it reports through the Prussian blue similar object entrance of electrostatic spinning Co-Fe
It is multiple that nitrogen-doped carbon nano-fiber made from polyacrylonitrile fibre and the mode being further heat-treated coats Fe-Co alloy/C nano particle
Condensation material and its in alkaline medium to the electrocatalysis characteristic of oxygen reduction reaction；(3) 2018 years " Journal of the
Electrochemical Society " it reports with FeCl3、CoCl2It is total for the Fe/Co/P of precursor preparation with phytic acid
Adulterate porous C catalyst and its in alkaline medium to the electrocatalysis characteristic of oxygen reduction reaction；(4) 2017 years " ACS
Applied Materials & Interfaces " it reports with metalloporphyrin base MOFs, PCN-600-Ni and graphene oxidation
The Fe/Ni/P codope reduced graphene oxide serving catalyst and its electricity to oxygen evolution reaction that object is presoma and template preparation
Catalytic performance.However, it is related with sulfonation iron-phthalocyanine (FeTsPc) be external hetero atom source, introduced simultaneously on the basis of ZIF-67
Fe and S Fe, Co, N and S codope carbon composite catalyst and is applied to electrocatalytic oxidation reduction reaction to design synthesis
Research is there is not yet document and patent report.
Goal of the invention
The purpose of the present invention is in view of the deficiencies of the prior art, and provide a kind of bimetallic base Fe-Co-N-S codope carbon catalysis
Agent and the preparation method and application thereof.This method and process is simple, operating condition is mildly controllable, resulting materials excellent electrochemical performance
And it is low in cost, it has a good application prospect.
Realizing the technical solution of the object of the invention is:
A kind of preparation method of bimetallic base Fe-Co-N-S codope C catalyst, unlike the prior art, including it is as follows
Step:
1) 40 mg ZIF-67 are added in the container equipped with 20 mL ethyl alcohol, 2 mL is rapidly joined after ultrasonic disperse is uniform
The aqueous solution of FeTsPc, the mass ratio for controlling wherein ZIF-67/FeTsPc is 1/0.25-2, is centrifuged after 24 h of magnetic agitation dry
It is dry, obtain FeTsPc/ZIF-67 composite material；
2) composite sample that 120 mg step 1) obtain is weighed, is placed in quartz tube furnace under Ar atmosphere in 500-1000
DEG C heat treatment 3 h, obtain the i.e. Fe-Co-N-S-C of bimetallic base Fe-Co-N-S codope C catalyst.
Bimetallic base Fe-Co-N-S codope C catalyst, that is, Fe-Co-N-S-C made from above-mentioned preparation method.
Bimetallic base Fe-Co-N-S codope C catalyst, that is, Fe-Co-N-S-C made from above-mentioned preparation method is firing
Expect the application in cell cathode oxygen reduction reaction.
In M-N-C(M=Fe, Co) in catalyst system, by rationally designing and constructing its active bit architecture, it can be with
The performance to compare favourably with Pt base catalyst is shown, the structure of presoma is very crucial to the ORR performance of prepared catalyst.
In the technical program, with ZIF-67 and sulfonation iron-phthalocyanine (FeTsPc) for hetero atom presoma, pass through simple heat
Processing method prepares bimetallic base Fe-Co-N-S codope C catalyst, and the addition of FeTsPc significantly improves the heat of MOFs
Stability, the dispersibility of each ingredient is good with homogeneity in prepared catalyst, and exists strongly between each foreign atom
Electron transfer interaction, to significantly enhance the electro catalytic activity of catalyst towards oxygen reduction reaction.In addition, Fe-Co-N-
S codope C catalyst also shows electrochemical stability more better than business Pt/C and methanol tolerance performance.
This method and process is simple, operating condition is mildly controllable, resulting materials excellent electrochemical performance and low in cost, tool
There is good application prospect.
Detailed description of the invention
Fig. 1 is the flow diagram that Fe-Co-N-S codope C catalyst is prepared in embodiment；
Fig. 2 is the SEM figure of the Fe-Co-N-S codope C catalyst prepared in embodiment；
Fig. 3 is the TEM figure of the Fe-Co-N-S codope C catalyst prepared in embodiment；
Fig. 4 is the Co-N-C prepared in embodiment, and Fe-Co-N-C, Fe-Co-N-S-C and business Pt/C catalyst are in O2Saturation
Linear sweep voltammetry curve graph in 0.1 M KOH solution；
Fig. 5 is the Fe-Co-N-S-C prepared in embodiment and business Pt/C catalyst in O2Saturation 0.1 M KOH solution in
0.3 VRHEThe lower chronoa mperometric plot figure for carrying out methanol tolerance test.
Specific embodiment
The contents of the present invention are further elaborated with reference to the accompanying drawings and examples, but are not to limit of the invention
It is fixed.
Embodiment:
Referring to Fig.1, a kind of preparation method of bimetallic base Fe-Co-N-S codope C catalyst, includes the following steps:
1) 40 mg ZIF-67 are added in the container equipped with 20 mL ethyl alcohol, 2 mL is rapidly joined after ultrasonic disperse is uniform
The aqueous solution of FeTsPc, the mass ratio for controlling wherein ZIF-67/FeTsPc is 1/0.25-2, is centrifuged after 24 h of magnetic agitation dry
It is dry, obtain FeTsPc/ZIF-67 composite material；
2) composite sample that 120 mg step 1) obtain is weighed, is placed in quartz tube furnace under Ar atmosphere in 500-1000
DEG C heat treatment 3 h, obtain the i.e. Fe-Co-N-S-C of bimetallic base Fe-Co-N-S codope C catalyst.
Bimetallic base Fe-Co-N-S codope C catalyst, that is, Fe-Co-N-S-C made from above-mentioned preparation method.
Bimetallic base Fe-Co-N-S codope C catalyst, that is, Fe-Co-N-S-C made from above-mentioned preparation method is firing
Expect the application in cell cathode oxygen reduction reaction.
SEM and tem analysis obtain, and this example MOFs structure after Overheating Treatment does not occur significantly destroying and reuniting existing
As, show that the addition of FeTsPc improves the thermal stability of MOFs, in prepared catalyst each ingredient dispersibility with it is uniform
Property is good, in addition, can also see on the surface of bimetallic base Fe-Co-N-S codope C catalyst made from this example preparation method
Observe equally distributed black particle, STEM the result shows that predominantly metal Co and Co oxide, about 25 nm of partial size or so,
As shown in Figures 2 and 3.
XPS analysis points out, Fe-Co- in bimetallic base Fe-Co-N-S codope C catalyst made from this example preparation method
N 1s and Co the 2p peak position of N-S-C is born respectively compared with the analog value of Co-N-C and has moved 0.2 eV and shuffled 1.1 eV, shows
There are strong electron transfer interactions between foreign atom in Fe-Co-N-S-C catalyst, this is conducive to enhance the catalysis
Electrocatalysis characteristic of the agent to oxygen reduction reaction.
As linear sweep voltammetry compare this example preparation method made from bimetallic base Fe-Co-N-S codope carbon,
Fe-Co-N-C, Co-N-C and business Pt/C catalyst are in alkaline medium to the electrocatalysis characteristic of oxygen reduction reaction.As a result
Out, bimetallic base Fe-Co-N-S codope C catalyst made from this example preparation method is close to the carrying current of oxygen reduction reaction
Degree is 6.46 mA cm-2, hence it is evident that the 5.25 mA cm-2 and business of 5.39 mA cm-2, Co-N-C higher than Fe-Co-N-C
5.32 mA cm-2 of Pt/C catalyst, in addition, bimetallic base Fe-Co-N-S codope carbon made from this example preparation method is catalyzed
The half wave potential of agent is 0.856 V, can almost be compared favourably with 0.866 V of half wave potential of business Pt/C catalyst.These knots
Fruit shows bimetallic base Fe-Co-N-S codope C catalyst made from this example preparation method in alkaline medium to hydrogen reduction
Reaction shows excellent electro catalytic activity, as shown in Figure 4.
It has carried out methanol tolerance performance by chronoamperometry to compare, as shown in figure 5, rapidly joining 2 M first in 250 s or so
After alcoholic solution, the current density of business Pt/C catalyst sharply declines, and bimetallic base Fe- made from this example preparation method
The current density of Co-N-S codope C catalyst illustrates bimetallic base made from this example preparation method there is no significant change
Fe-Co-N-S codope C catalyst has excellent methanol tolerance performance.
Claims (3)
1. a kind of preparation method of bimetallic base Fe-Co-N-S codope C catalyst, characterized in that include the following steps:
1) 40 mg ZIF-67 are added in the container equipped with 20 mL ethyl alcohol, 2 mL is rapidly joined after ultrasonic disperse is uniform
The aqueous solution of FeTsPc, the mass ratio for controlling wherein ZIF-67/FeTsPc is 1/0.25-2, is centrifuged after 24 h of magnetic agitation dry
It is dry, obtain FeTsPc/ZIF-67 composite material；
2) composite sample that 120 mg step 1) obtain is weighed, is placed in quartz tube furnace under Ar atmosphere in 500-1000
DEG C heat treatment 3 h, obtain the i.e. Fe-Co-N-S-C of bimetallic base Fe-Co-N-S codope C catalyst.
2. bimetallic base Fe-Co-N-S codope C catalyst, that is, Fe-Co-N- made from the preparation method described in claim 1
S-C。
3. bimetallic base Fe-Co-N-S codope C catalyst, that is, Fe-Co-N-S-C is in fuel battery negative pole described in claim 2
Application in oxygen reduction reaction.
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Cited By (4)
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| CN111354951A (en) * | 2020-02-28 | 2020-06-30 | 江苏大学 | Synthetic method and application of metal sulfide material based on encapsulated porphyrin |
| CN112038646A (en) * | 2020-09-14 | 2020-12-04 | 陈建夫 | Preparation method of catalyst for methanol fuel cell |
| CN114256470A (en) * | 2021-12-22 | 2022-03-29 | 合肥师范学院 | Cobalt-iron alloy nano-particles based on hollow cubic carbon material and preparation method and application thereof |
| CN114784299A (en) * | 2022-05-27 | 2022-07-22 | 中国第一汽车股份有限公司 | Nitrogen-sulfur doped carbon material and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111354951A (en) * | 2020-02-28 | 2020-06-30 | 江苏大学 | Synthetic method and application of metal sulfide material based on encapsulated porphyrin |
| CN112038646A (en) * | 2020-09-14 | 2020-12-04 | 陈建夫 | Preparation method of catalyst for methanol fuel cell |
| CN112038646B (en) * | 2020-09-14 | 2022-05-27 | 贵州六维新能源股份有限公司 | Preparation method of catalyst for methanol fuel cell |
| CN114256470A (en) * | 2021-12-22 | 2022-03-29 | 合肥师范学院 | Cobalt-iron alloy nano-particles based on hollow cubic carbon material and preparation method and application thereof |
| CN114256470B (en) * | 2021-12-22 | 2023-11-10 | 合肥师范学院 | Cobalt-iron alloy nanoparticle based on hollow cube carbon material and preparation method and application thereof |
| CN114784299A (en) * | 2022-05-27 | 2022-07-22 | 中国第一汽车股份有限公司 | Nitrogen-sulfur doped carbon material and preparation method and application thereof |
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Application publication date: 20191112 |