CN107146893A - A kind of preparation method of hetero atom original position doping carbon-supported catalysts and its application in a fuel cell - Google Patents
A kind of preparation method of hetero atom original position doping carbon-supported catalysts and its application in a fuel cell Download PDFInfo
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- CN107146893A CN107146893A CN201710387692.3A CN201710387692A CN107146893A CN 107146893 A CN107146893 A CN 107146893A CN 201710387692 A CN201710387692 A CN 201710387692A CN 107146893 A CN107146893 A CN 107146893A
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- catalyst
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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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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- 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
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Abstract
A kind of preparation method of doping carbon-supported catalysts in hetero atom original position involved in the present invention and its application in a fuel cell, while also developing a kind of method that simplicity constructs efficient loose structure catalyst using Heteroatom doping.In the preparation process of usual oxygen reduction catalyst in heteroatomic doping based on single adulterate, and Heteroatom doping is inefficient, causes its electro catalytic activity of the catalyst of synthesis to improve unobvious.Doping in situ is carried out in the present invention to hetero atom, and heteroatomic dopant species are flexible and changeable, while doping efficiency is high.Using the influence of cloud density between hetero atom, the non-metallic cathode oxygen reduction catalyst for possessing extensive use and large-scale production prospect has been synthesized.Preparation method technique of the present invention is simple, and suitable for the large-scale production of catalyst, the catalyst in the basic conditions, shows preferable oxygen reduction activity and stability.
Description
1. technical field
The present invention relates to a kind of hetero atom original position doping carbon-supported catalysts preparation method and its in a fuel cell should
Technical field, more particularly to a kind of ionic liquid forerunner without templated synthesis loose structure catalyst and many Heteroatom dopings
The synthetic method of body and its application technology as fuel battery cathod catalyst.
2. background technology
Fuel cell, to solving current problems faced, realizes the various of the energy because having the advantages that high efficiency, no pollution
Change is significant, therefore receives the extensive concern of researcher.Hydrogen reduction (ORR) is the important electrode reaction of fuel cell, by
Slow in its kinetics, activation energy height is, it is necessary to promote the generation of oxygen reduction reaction using Pt bases catalyst, it has also become limit
Make the key factor of this kind of energy.So exploitation is efficient, cheap catalyst is a stern challenge, mainly there is two big at present
Class a, class is the transition metal (Fe, Co, Ni etc.) enriched in the earth's crust；Another kind of is N containing hetero atom, B, S, P etc. carbon material.
From actual angle, the optimal case of solution is then to use non-metallic catalyst.
In recent years the carbon material of metal-free Heteroatom doping, because it has high catalytic activity, long-term stability
With cheap raw material by extensive concern.The CNT of the carbon material of various Heteroatom dopings such as N doping, the stone of N doping
Black alkene also has very high catalytic activity as oxygen reduction catalyst.However, the catalyst activity of existing Heteroatom doping and stably
Property need further raising, hetero atom can be carried out in the ionic liquid developed as Green Chemistry is risen doping in situ and
Zwitterion structure is adjustable extensively, thus active catalyst sites made from the ionic liquid of this kind of Heteroatom doping made is close
Degree is bigger.
This patent is proposed a kind of easy route and goes synthesis to be adulterated using hetero atom original position and obtain carbon-based hydrogen reduction and urge
Agent, and can be with the catalytic activity of catalyst with this variety of Heteroatom dopings.The obtained in this way sample of profit have than
The features such as surface area is big, avtive spot exposure is abundant, while a kind of method of simple synthesizing porous structure catalyst is also developed,
Obtain the non-metallic catalyst of function admirable.
3 content of the invention
Present invention aims at the carbon material that a kind of hetero atom original position is adulterated is developed, applied to fuel battery negative pole oxygen also
Morphology controllable and Heteroatom doping are flexible and changeable in original, the catalyst preparation process, have very big to the raising of catalytic activity
Help.
The present invention is achieved through the following technical solutions.
A kind of synthetic method of hetero atom original position doping carbon-supported catalysts, comprises the following steps：
The synthesis of step 1. presoma containing hetero atom；
Step 2. carries out pyrolysis processing to the material of above-mentioned synthesis under an inert atmosphere, obtains catalysis material；
Sample is made in above-mentioned catalysis material grind into powder by step 3..
Moreover, the material in the step 1 in presoma as cation is 1- methylimidazoles, 1- vinyl imidazoles, three
At least one of poly cyanamid, urea, pyridine, polyvinylpyrrolidone etc., are sulfuric acid, nitric acid, phosphorus as the material of anion
Mixture more than one or both of acid, dimethyl phosphate, fluoboric acid, boric acid, benzene sulfonic acid, terephthalic acid (TPA), hydrochloric acid etc..
Moreover, pyrolysis temperature is 400~1100 degrees Celsius in presoma in the step 2.
The catalysis material synthesized in the present invention is applied to cathodic oxygen reduction.
4 brief description of the drawings
Fig. 1 is the production hydrogen test result of the catalyst for preparing in 0.1mol saturation nitrogen KOH solutions in embodiment one.
5 embodiments
4 most preferred embodiments of the invention given below.
Embodiment one：
(1) 0.1mol 1- methylimidazoles are added in single-necked flask, 0.1mol sulfuric acid acid, normal temperature is then slowly added dropwise
1h is stirred, 50 DEG C is warming up to and stirs 4h, obtain viscous liquid.
(2) take a part of above-mentioned viscous liquid, in tube furnace using N2 as protection gas carry out pyrolysis processing, first with 1h from
Room temperature rises to 100 degrees Celsius, then with 5 DEG C/min be warming up to 560 DEG C calcining one hour after natural cooling, obtain black solid.
(3) 7.5mg after above-mentioned solid abrasive, will be taken to be mixed with 150 μ LNafion solution and 1350 μ L ethanol solutions
Match somebody with somebody to obtain catalyst slurry after ultrasound 1h afterwards, take 10 μ L slurries to be added drop-wise on glass-carbon electrode, electro-chemical test is carried out after drying 3h, it is main
There are cyclic voltammetric (CV), linear scan (LSV), AC impedance (EIS) etc..
(4) after test terminates, it is found that the catalyst prepared also has preferably production hydrogen activity (see Fig. 1).
Embodiment two：
(1) 1- methylimidazoles, 1- vinyl imidazoles, melamine, urea, pyridine, polyethylene are added in single-necked flask
At least one of pyrrolidones etc., is then slowly added dropwise equimolar sulfuric acid, and stirring at normal temperature 1h is warming up to 50 DEG C and stirred
4h, obtains viscous liquid.
(2) take a part of above-mentioned viscous liquid, in tube furnace using N2 as protection gas carry out pyrolysis processing, first with 1h from
Room temperature rises to 100 degrees Celsius, then with 5 DEG C/min be warming up to 560 DEG C calcining one hour after natural cooling, obtain black solid.
(3) 7.5mg after above-mentioned solid abrasive, will be taken to be mixed with 150 μ L Nafion solutions and 1350 μ L ethanol solutions
Match somebody with somebody to obtain catalyst slurry after ultrasound 1h afterwards, take 10 μ L slurries to be added drop-wise on glass-carbon electrode, electro-chemical test is carried out after drying 3h, it is main
There are cyclic voltammetric (CV), linear scan (LSV), AC impedance (EIS) etc..
Embodiment three：
(1) 1- vinyl imidazoles are added in single-necked flask, equimolar dimethyl phosphate, fluorine boron is then slowly added dropwise
Mixture more than one or both of acid, benzene sulfonic acid, terephthalic acid (TPA) etc., stirring at normal temperature 1h is warming up to 50 DEG C and stirred
4h, obtains viscous liquid.
(2) take a part of above-mentioned viscous liquid, in tube furnace using N2 as protection gas carry out pyrolysis processing, first with 1h from
Room temperature rises to 100 degrees Celsius, then with 5 DEG C/min be warming up to 560 DEG C calcining one hour after natural cooling, obtain black solid.
(3) 7.5mg after above-mentioned solid abrasive, will be taken to be mixed with 150 μ L Nafion solutions and 1350 μ L ethanol solutions
Match somebody with somebody to obtain catalyst slurry after ultrasound 1h afterwards, take 10 μ L slurries to be added drop-wise on glass-carbon electrode, electro-chemical test is carried out after drying 3h, it is main
There are cyclic voltammetric (CV), linear scan (LSV), AC impedance (EIS) etc..
Example IV：
(1) 1- vinyl imidazoles are added in single-necked flask, equimolar sulfuric acid, nitric acid, phosphoric acid, boron is then slowly added dropwise
Mixture more than one or both of acid, hydrochloric acid etc., stirring at normal temperature 1h is warming up to 50 DEG C and stirs 4h, obtains thick liquid
Body.
(2) take a part of above-mentioned viscous liquid, in tube furnace using N2 as protection gas carry out pyrolysis processing, first with 1h from
Room temperature rises to 100 degrees Celsius, then with 5 DEG C/min be warming up to 560 DEG C calcining one hour after natural cooling, obtain black solid.
(3) 7.5mg after above-mentioned solid abrasive, will be taken to be mixed with 150 μ L Nafion solutions and 1350 μ L ethanol solutions
Match somebody with somebody to obtain catalyst slurry after ultrasound 1h afterwards, take 10 μ L slurries to be added drop-wise on glass-carbon electrode, electro-chemical test is carried out after drying 3h, it is main
There are cyclic voltammetric (CV), linear scan (LSV), AC impedance (EIS) etc..
Claims (3)
1. a kind of preparation method of hetero atom original position doping carbon-supported catalysts and its application in a fuel cell
It is characterized in that：
During precursor synthesis as zwitterion material mol ratio be 1: 100~100: 1.
2. according to claim 3, it is characterised in that：In step 1 during precursor synthesis, zwitterion material is by a certain percentage
It is added drop-wise in round-bottomed flask, 2~18h of water-bath under conditions of 30~100 degrees Celsius.
3. according to claim 3, it is characterised in that：In step 2 inert atmosphere be nitrogen, helium, argon gas in one kind or
Two or more mixed gas；Pyrolysis temperature is 400~1100 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707337A (en) * | 2019-09-29 | 2020-01-17 | 中国石油大学(华东) | Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106374117A (en) * | 2016-11-25 | 2017-02-01 | 天津工业大学 | Preparation of N and P co-doped nonmetallic oxygen reduction catalyst |
| CN106558707A (en) * | 2016-11-25 | 2017-04-05 | 天津工业大学 | A kind of preparation and the application as oxygen reduction reaction non-metallic catalyst of curling nanometer carbon plate |
| CN106784885A (en) * | 2016-11-30 | 2017-05-31 | 天津工业大学 | A kind of curling nanometer carbon plate that nitrogen phosphorus is co-doped with prepare and as non-metallic catalyst oxygen reduction reaction application |
| CN107017410A (en) * | 2017-03-21 | 2017-08-04 | 海安南京大学高新技术研究院 | Oxygen reduction catalyst and preparation method thereof, oxygen reduction electrode and fuel cell |
-
2017
- 2017-05-23 CN CN201710387692.3A patent/CN107146893A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106374117A (en) * | 2016-11-25 | 2017-02-01 | 天津工业大学 | Preparation of N and P co-doped nonmetallic oxygen reduction catalyst |
| CN106558707A (en) * | 2016-11-25 | 2017-04-05 | 天津工业大学 | A kind of preparation and the application as oxygen reduction reaction non-metallic catalyst of curling nanometer carbon plate |
| CN106784885A (en) * | 2016-11-30 | 2017-05-31 | 天津工业大学 | A kind of curling nanometer carbon plate that nitrogen phosphorus is co-doped with prepare and as non-metallic catalyst oxygen reduction reaction application |
| CN107017410A (en) * | 2017-03-21 | 2017-08-04 | 海安南京大学高新技术研究院 | Oxygen reduction catalyst and preparation method thereof, oxygen reduction electrode and fuel cell |
Non-Patent Citations (1)
| Title |
|---|
| JIAN GAO，等: "Polymerizable ionic liquid-derived carbon for oxygen reduction and evolution", 《J APPL ELECTROCHEM》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707337A (en) * | 2019-09-29 | 2020-01-17 | 中国石油大学(华东) | Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst |
| CN110707337B (en) * | 2019-09-29 | 2022-04-08 | 中国石油大学(华东) | Preparation method and application of carbon-based non-noble metal oxygen reduction catalyst |
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Application publication date: 20170908 |