CN106374117A - Preparation of N and P co-doped nonmetallic oxygen reduction catalyst - Google Patents

Preparation of N and P co-doped nonmetallic oxygen reduction catalyst Download PDF

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Publication number
CN106374117A
CN106374117A CN201611074978.8A CN201611074978A CN106374117A CN 106374117 A CN106374117 A CN 106374117A CN 201611074978 A CN201611074978 A CN 201611074978A CN 106374117 A CN106374117 A CN 106374117A
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doped
catalyst
oxygen reduction
preparation
nitrogen
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CN201611074978.8A
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Chinese (zh)
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高建
李成松
苏昊文
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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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
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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

Abstract

The invention relates to preparation of an oxygen reduction catalyst for nitrogen and phosphorus co-doped carbon material with anion functionalization ionic liquid as the precursor. A traditional similar material is generally only doped with nitrogen, and though the catalyst has certain catalytic performance, the performance still remains to improve. By means of the catalyst, nitrogen and phosphorus co-doped carbon material can be obtained; due to the common effect of N and P, the catalytic performance of the catalyst is remarkably improved.

Description

A kind of n, p are co-doped with the preparation of Nonmetal oxygen reduction catalyst
1. technical field
A kind of n, p are co-doped with preparation and the application as oxygen reduction reaction non-metallic catalyst of Carbon Materials.
2. background technology
Carried with alleviating the energy and consuming in a large number it is necessary to find a kind of new energy in today that energy demand day is becoming tight The environment coming and energy problem.Due to having higher energy density and relatively low pollutant emission, metal-air battery and combustion Material battery is considered as that one kind has more potential new substitute electric power.No matter for metal-air battery or fuel electricity Pond, occurs the oxygen reduction reaction in negative electrode to be all a kind of important electrode reaction (chang, c.；Wen, t.an investigation of thermally prepared electrodes for oxygen reduction in Alkaline solution.mater.chem.phys.1997,47,203.), the normal operation to battery plays a key effect, But its reaction activity is higher, reaction is difficult, for reducing reaction activity, promotes electrode reaction it is necessary to adopted your gold substantial amounts of Metal catalyst, particularly pt catalyst, to ensure the normal work of battery.Because this kind of noble metal reserves rareness is expensive, Lead to this kind of power supply relatively costly, so as to be difficult to large-scale use.For this problem, existing Many researchers have been done in a large number Work attempts to reduce noble metal carrying capacity, but final solution still finds non-noble metal catalyst catalyst as an alternative (chen, z.w.；Higgins, d.；Yu, a.p.；Zhang, l.；Zhang, j.j.a review on non-precious Metal electrocatalysts for pem fuel cells.energy environ.sci.2011,4,3167).
(jasinski.a new fuel cell since the sixties in last century begins one's study non-precious metal catalyst Cathode catalyst.nature 1964,201,1212), have been developed over multiple possible non-precious metal catalysts, its In a kind of most promising non-precious metal catalyst become based on the nitrating material with carbon element of metal-oxide, but this kind of catalyst Performance need to improve further.In addition to above-mentioned metallic catalyst, the in addition non-metal catalyst of a class nitrating material with carbon element Receive significant attention.
In recent years, there is the nitrating material with carbon element such as nitrogen doped carbon nanotube of certain microstructure, nitrogen-doped graphene etc. is as oxygen Reduction non-metallic catalyst receive significant attention in recent years (gong, k., du, f., xia, z., durstock, m.＆dai, l.nitrogen-doped carbon nanotube arrays with high electrocatalytic activity For oxygen reduction.science 323,760-764 (2009) .liu, r., wu, d., feng, x.＆m ü llen, k.nitrogen-doped ordered mesoporous graphitic arrays with high Electrocatalytic activity for oxygen reduction.angew.chem.int.ed.49,2565-2569 (2010) .wang, s.et al.bcn graphene as efficient metal-free electrocatalyst for The oxygen reduction reaction.angew. chem.int.ed.51,209-4212 (2012) but. nonmetallic The performance of catalyst also goes out to develop non-metallic catalyst it is necessary to enter one than relatively low at present.
In addition to common nitrating Carbon Materials, the Carbon Materials that n, p are co-doped with are also the important non-metallic catalyst of a class (wang, s.et al.vertically aligned bcn nanotubes as efficient metal-free Electrocatalysts for the oxygen reduction reaction:a synergetic effect by co- Doping with boron and nitrogen.angew.chem.int.ed.50,11756-11760 (2011) .15.liang, j., jiao, y., jaroniec, m.＆qiao, s.z.sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically Enhanced performance.angew.chem.int.ed.51,11496-11500 (2012) .16.xue, y.et Al.three-dimensional b, n-doped graphene foam as a metal-free catalyst for Oxygen reduction reaction.phys.chem.chem.phys.15,12220-12226 (2013) .17.jiao, Y., zheng, y., jaroniec, m.＆qiao, s.z.origin of the electrocatalytic oxygen Reduction activity of graphene-based catalysts:a roadmap to achieve the best Performance.j.am.chem.soc.136,4394-4403 (2014) .).Prepare this kind of material and generally require charcoal, n, p tri- Plant presoma, preparation process is complicated.
This patent purpose is to propose a kind of preparation of the ionic liquid of functionalization, and as n, c, p presoma prepares nitrogen, phosphorus The material with carbon element being co-doped with.Electro-chemical test is bright, and the sample that this method is obtained has preferable oxygen reduction catalytic activity.
3 content of the invention
Present invention aim at a kind of inexpensive, eco-friendly n of exploitation, the material with carbon element that p is co-doped with, urge for use as nonmetallic Agent presoma.
The present invention is accomplished by.
A kind of poly ion liquid of pore-creating functionalization, it comprises the following steps:
By acid reaction phosphorous with certain to imidazoles or pyridine, this acid can be the phosphoric acid such as phosphoric acid, phosphotungstic acid to step 1.；
Above-mentioned solid is carried out calcining 1～4h in 500～1000 DEG C of environment, under inert gas shielding by step 2., cooling Obtain carbonized product afterwards
Step 3., by above-mentioned product grind into powder, obtains final product.
4 brief descriptions
Linear scanning test result that Fig. 1 obtains for material prepared by this patent in 0.1m koh aqueous solution it is seen that its Play real current potential and can reach 0.95vrhe, the take-off potential (～1v) of platinum (pt/c) catalyst is carried very close to conventional charcoal.
5 specific embodiments
5 most preferred embodiments of the present invention given below.
Embodiment one:
(1) add 0.1mol vinyl imidazole in single-necked flask, be subsequently added 0.05mol phosphoric acid, stirring at normal temperature 2 hours Wait, be warming up to 50 DEG C and be stirred overnight, obtain thick liquid.
(2) aforesaid liquid body is taken out, put in porcelain boat, calcine in tube furnace, with n2For shielding gas, 500 DEG C of calcinings Temperature fall after two hours, obtains black fluffy solid.
(4) ultrasonic shake after 5mg after above-mentioned solid abrasive, being taken to mix with 100 μ lnafion solution and 900 μ l ethanol solution Catalyst slurry is obtained after swinging 30 minutes, takes 10 μ l serosity to be added drop-wise on glass-carbon electrode, be dried 2 and as a child carried out electrochemistry survey Examination, mainly has cyclic voltammetric, linear scanning etc..
Embodiment two:
(1) add 0.1mol allyl imidazole in single-necked flask, be subsequently added 0.1mol phosphoric acid, stirring at normal temperature 2 hours Wait, be warming up to 50 DEG C and be stirred overnight, obtain thick liquid.
(2) aforesaid liquid is taken out, put in porcelain boat, calcine in tube furnace, with n2For shielding gas, 550 DEG C of calcinings two Temperature fall after hour, obtains black fluffy solid.
(4) ultrasonic shake after 5mg after above-mentioned solid abrasive, being taken to mix with 100 μ lnafion solution and 900ul ethanol solution Catalyst slurry is obtained after swinging 30 minutes, takes 10 μ l serosity to be added drop-wise on glass-carbon electrode, be dried 2 and as a child carried out electrochemistry survey Examination, mainly has cyclic voltammetric, linear scanning etc..
Embodiment three:
(1) add 0.1mol 1-butylene base imidazoles in single-necked flask, be subsequently added 0.1mol phosphoric acid, stirring at normal temperature 2 is little When, it is warming up to 50 DEG C and is stirred overnight, obtain thick liquid.
(2) aforesaid liquid is taken out, put in porcelain boat, calcine in tube furnace, with n2For shielding gas, 550 DEG C of calcinings two Temperature fall after hour, obtains black fluffy solid.
(4) ultrasonic shake after 5mg after above-mentioned solid abrasive, being taken to mix with 100 μ lnafion solution and 900 μ l ethanol solution Catalyst slurry is obtained after swinging 30 minutes, takes 10 μ l serosity to be added drop-wise on glass-carbon electrode, be dried 2 and as a child carried out electrochemistry survey Examination, mainly has cyclic voltammetric, linear scanning etc..
Example IV:
(1) add 0.1mol 1-butylene base imidazoles in single-necked flask, be subsequently added 0.1mol phosphoric acid, stirring at normal temperature 2 is little When, it is warming up to 50 DEG C and is stirred overnight, obtain thick liquid.
(2) aforesaid liquid is taken out, put in porcelain boat, calcine in tube furnace, with n2For shielding gas, 850 DEG C of calcinings two Temperature fall after hour, obtains black fluffy solid.
(4) ultrasonic shake after 5mg after above-mentioned solid abrasive, being taken to mix with 100 μ lnafion solution and 900 μ l ethanol solution Catalyst slurry is obtained after swinging 30 minutes, takes 10 μ l serosity to be added drop-wise on glass-carbon electrode, be dried 2 and as a child carried out electrochemistry survey Examination, mainly has cyclic voltammetric, linear scanning etc..
Embodiment five:
(1) add 0.1mol 1-butylene base imidazoles in single-necked flask, be subsequently added 0.1mol phosphotungstic acid, stirring at normal temperature 2 As a child, it is warming up to 50 DEG C and is stirred overnight, obtain thick liquid.
(2) aforesaid liquid is taken out, put in porcelain boat, calcine in tube furnace, with n2For shielding gas, 850 DEG C of calcinings two Temperature fall after hour, obtains black fluffy solid.
(4) ultrasonic shake after 5mg after above-mentioned solid abrasive, being taken to mix with 100 μ lnafion solution and 900 μ l ethanol solution Catalyst slurry is obtained after swinging 30 minutes, takes 10 μ l serosity to be added drop-wise on glass-carbon electrode, be dried 2 and as a child carried out electrochemistry survey Examination, mainly has cyclic voltammetric, linear scanning etc..

Claims (2)

1. a kind of n, p are co-doped with the preparation of Nonmetal oxygen reduction catalyst
It is characterized in that:
Employ vinyl imidazole and the allyl imidazole that cation contains polymerizable functional group, anion is phosphorous ionic liquid Body, this ionic liquid can realize n in calcination process, and p is co-doped with, it is hereby achieved that the material with carbon element containing phosphorus and nitrogen, electricity Test chemical shows that this product has the high performance of oxygen-reducing catalyst of comparison.
2. as claimed in claim 1, experimental procedure is as follows:
The ionic liquid of step 1. complex functionality；
Above-mentioned intermediate is calcined in the range of 500～950 DEG C by step 2. under nitrogen protection, obtains final product.
CN201611074978.8A 2016-11-25 2016-11-25 Preparation of N and P co-doped nonmetallic oxygen reduction catalyst Pending CN106374117A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910908A (en) * 2017-03-21 2017-06-30 海安南京大学高新技术研究院 Oxygen reduction catalyst and preparation method thereof, oxygen reduction electrode and battery
CN107146893A (en) * 2017-05-23 2017-09-08 天津工业大学 A kind of preparation method of hetero atom original position doping carbon-supported catalysts and its application in a fuel cell
CN108609602A (en) * 2018-05-18 2018-10-02 中国工程物理研究院化工材料研究所 Nitrogen doped micropore carbon material and preparation method thereof based on the poly ion liquid containing energy
CN108630954A (en) * 2018-05-09 2018-10-09 天津工业大学 A method of it preparing high-specific surface area nitrogen phosphorus and is co-doped with carbon material
CN109494378A (en) * 2018-12-12 2019-03-19 齐齐哈尔大学 A kind of preparation method of the catalyst for catalytic fuel cell cathode reaction

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105879895A (en) * 2016-04-27 2016-08-24 天津工业大学 Nitrogen-doped porous carbon nanosheet-supported non-noble metal catalyst and preparation method thereof
CN106000438A (en) * 2016-06-03 2016-10-12 兰州交通大学 Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105879895A (en) * 2016-04-27 2016-08-24 天津工业大学 Nitrogen-doped porous carbon nanosheet-supported non-noble metal catalyst and preparation method thereof
CN106000438A (en) * 2016-06-03 2016-10-12 兰州交通大学 Preparation method and application of nitrogen and phosphorus co-doped porous carbon materials

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106910908A (en) * 2017-03-21 2017-06-30 海安南京大学高新技术研究院 Oxygen reduction catalyst and preparation method thereof, oxygen reduction electrode and battery
CN107146893A (en) * 2017-05-23 2017-09-08 天津工业大学 A kind of preparation method of hetero atom original position doping carbon-supported catalysts and its application in a fuel cell
CN108630954A (en) * 2018-05-09 2018-10-09 天津工业大学 A method of it preparing high-specific surface area nitrogen phosphorus and is co-doped with carbon material
CN108609602A (en) * 2018-05-18 2018-10-02 中国工程物理研究院化工材料研究所 Nitrogen doped micropore carbon material and preparation method thereof based on the poly ion liquid containing energy
CN108609602B (en) * 2018-05-18 2020-01-31 中国工程物理研究院化工材料研究所 Nitrogen-doped microporous carbon material based on energetic polyion liquid and preparation method thereof
CN109494378A (en) * 2018-12-12 2019-03-19 齐齐哈尔大学 A kind of preparation method of the catalyst for catalytic fuel cell cathode reaction
CN109494378B (en) * 2018-12-12 2021-08-24 齐齐哈尔大学 Preparation method of catalyst for catalyzing cathode reaction of fuel cell

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Application publication date: 20170201