CN110492117A - A kind of double ligand strategies prepare non noble metal oxygen reduction elctro-catalyst - Google Patents
A kind of double ligand strategies prepare non noble metal oxygen reduction elctro-catalyst Download PDFInfo
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- CN110492117A CN110492117A CN201910798129.4A CN201910798129A CN110492117A CN 110492117 A CN110492117 A CN 110492117A CN 201910798129 A CN201910798129 A CN 201910798129A CN 110492117 A CN110492117 A CN 110492117A
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- oxygen reduction
- reduction reaction
- base metal
- elctro
- 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
- H01M4/96—Carbon-based electrodes
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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
Abstract
The present invention relates to a kind of base metal elctro-catalysts with double ligand strategy preparations for acid oxygen reduction reaction.A kind of iron, nitrogen, the equally distributed metal organic frame polymer of carbon have been synthesized by method simple and easy to get, and has been prepared for the acid oxygen reduction catalyst of Fe-Nx/C type by high temperature cabonization.This method, as source metal, regulates and controls the activity of catalyst hydrogen reduction by content of the two kinds of organic ligands of regulation in metal organic frame polymer using zinc salt and molysite.The material not only simple synthetic method, low raw-material cost, but also there is efficient oxygen reduction activity and preferable stability under acidity.
Description
Technical field
Invention is related to the preparation process of the base metal elctro-catalyst with double ligand strategies for oxygen reduction reaction, specifically
It is related to a kind of utilize to be coordinated containing double ligand organo units and metal, then aggregated and high temperature cabonization, which is pyrolyzed to obtain, has hydrogen reduction
The elctro-catalyst of catalytic performance has broad application prospects in fuel cell field.
Background technique
Proton Exchange Membrane Fuel Cells is because of its high conversion, environmental-friendly, hardly discharge nitrogen oxide and sulphur oxygen
Compound, it is considered to be one of most promising energy storage and conversion equipment.Proton Exchange Membrane Fuel Cells is with pure hydrogen
It is fuel as anode reaction substance, using pure oxygen as cathode reactant, hydrogen ion is sent out by proton exchange membrane and cathode gas phase
Life reacts and releases electric energy.Wherein the slow dynamics of Cathodic oxygen reduction is the principal element of fuel cell performance,
Therefore excellent oxygen reduction catalyst is needed to be catalyzed.
The electro-catalysis of fuel battery negative pole hydrogen reduction at present is based on the noble metals such as Pt and its alloy.Although precious metals pt is catalyzed
The hydrogen reduction catalytic performance of agent is high, but it is expensive, scarcity of resources, stability are poor, limits its commercialized development and application.
Research shows that the progress that carbon material after functionalization can be reacted with catalytic oxidation-reduction, by double ligand strategies adulterate base metal,
The elctro-catalyst that nitrogen-atoms is prepared not only has efficient hydrogen reduction catalytic performance, but also low raw-material cost stability is high,
Therefore, it has become the important research directions of oxygen reduction catalyst for the atom doped carbon material catalyst of base metal.However, doping
Site is not apparent, and base metal atom, which is unevenly distributed, constrains further increasing for carbon material catalyst performance.
Summary of the invention
Technical problem solved by the invention is: mixing double ligands by double ligand strategies, compares between Effective Regulation ligand
Example regulates and controls aperture and the specific surface area of metal organic frame, and can effectively be coordinated with metal, improves doping number of sites
Amount, effectively improves catalytic performance.Metal organic frame obtained through high temperature cabonization and meanwhile have efficient hydrogen reduction catalytic performance with
Iron-nitrogen-carbonic acid oxygen reduction electro-catalyst of excellent stability, solves fuel battery cathod catalyst catalytic performance not
Height, stability is poor, the problem of being difficult to large-scale promotion at high cost.
The present invention is achieved in the following ways:
Step 1) directly synthesizes equally distributed metal organic frame polymer using two kinds of ligands and source metal.It weighs a certain amount of
Two kinds of ligands, be mixed and stirred for uniformly being scattered in it in solvent, a certain amount of two kinds of metal salts be added, wherein metal is distinguished
It is dissolved with solvent, is added after being uniformly dispersed, reaction a period of time, washed with solvent, filter to obtain precipitating.It is placed in baking oven and dries i.e.
Obtain iron, nitrogen, the equally distributed metal organic frame polymer of carbon.
The equally distributed metal organic frame polymer of the iron, nitrogen, carbon of synthesis is transferred in porcelain boat by step 2, and is put into
Certain time is calcined in tube furnace at a certain temperature, the cooling base metal electricity up to for oxygen reduction reaction of Temperature fall is urged
Agent.
Further preferably
Molysite described in step 1) can be able to be Fe(NO3)39H2O, ferric chloride hexahydrate, six hydrated sulfuric acids Asia for the molysite
Iron ammonium, ferrous sulfate, ferric sulfate, Iron dichloride tetrahydrate, four are hydrated ferrous acetates, anhydrous frerrous chloride and anhydrous ferric chloride
It is one or two kinds of.
Zinc salt described in step 1) can be the one or two of zinc nitrate hexahydrate, zinc sulfate, zinc chloride and zinc acetate.
Two kinds of ligands described in step 1) can be methylimidazole, ethyl imidazol(e), benzimidazole, imidazoles, tri- nitrogen of 1,2,4-
Any two kinds in azoles, 6-chloropurine and benzotriazole.
The molar ratio of two kinds of ligands described in step 1) is 1:(1-5), it is preferably in a proportion of 1:(3-5).
The inert gas led in high temperature process furnances described in step 2 can be argon gas or nitrogen, gas flow 50-
120ml/min。
Calcination process is to be warming up to 150-200 with the rate of 1-10 DEG C/min in high temperature process furnances described in step 2
DEG C, keep the temperature 0.5-1.0 hours；It is warming up to 800-1000 DEG C with the rate of 1-5 DEG C/min again, keeps the temperature 1-3.0 hours.
Advantages of the present invention
The present invention utilizes double ligand strategies to be used for the base metal elctro-catalyst of oxygen reduction reaction, and synthetic method is simple, preparation
Elctro-catalyst not only has excellent hydrogen reduction catalytic performance, but also with good stability.To prepare fuel battery negative pole
Catalyst provides new thinking.Compared with the prior art, the invention has the following advantages that
1) present invention mixes two kinds of ligands by double ligand strategies, and can effectively be coordinated with metal, improves doping site
Quantity effectively improves catalytic performance, and ratio improves aperture and the specific surface area of metal organic frame between Effective Regulation ligand.
2) present invention prepares iron-nitrogen-carbon hydrogen reduction electro-catalysis of function admirable by one-step synthesis and step carbonization
Other catalyst are compared in agent, and experiment synthesis process is simple, low raw-material cost, and yield is high, effectively improve catalytic performance.
3) present invention prevents metallic particles to be corroded in harsh environment, mentions by regulating and controlling metal-doped amount, high temperature cabonization
High catalyst stability.
Detailed description of the invention
Fig. 1 is the base metal elctro-catalyst for oxygen reduction reaction that double ligand strategy synthesis are utilized in embodiment 1
Linear sweep voltammetry figure.
Fig. 2 is the base metal elctro-catalyst for oxygen reduction reaction that double ligand strategy synthesis are utilized in embodiment 2
Linear sweep voltammetry figure.
Fig. 3 is the base metal elctro-catalyst for oxygen reduction reaction that double ligand strategy synthesis are utilized in comparative example 1
Linear sweep voltammetry figure.
Fig. 4 is the base metal elctro-catalyst for oxygen reduction reaction that double ligand strategy synthesis are utilized in comparative example 2
Linear sweep voltammetry figure.
Fig. 5 is the base metal elctro-catalyst for oxygen reduction reaction that double ligand strategy synthesis are utilized in embodiment 1
Scanning electron microscope (SEM) photograph.
Specific embodiment
Embodiment 1
Step 1) weighs 1.8474g(22.5mmol) 2-methylimidazole, 1.1592g(7.5mmol) 6-chloropurine is added to and is equipped with
In the three-neck flask of 120ml methanol, ultrasonic 10min is to being uniformly dispersed.Weighing 2.9749g(10mmol) zinc nitrate hexahydrate is dissolved in
In 30ml methanol, 0.1352g(0.5mmol is weighed) it is dissolved in 1ml deionized water, until ultrasonic mixing is uniform.It is added to and is dissolved in nitre
In the methanol solution of sour zinc, ultrasonic mixing is uniformly distributed metallic solution, is added in three-neck flask, microwave reaction 1h.To anti-
It should terminate, filter, and washed with methanol and must precipitate three times.It is placed in baking oven to dry to take out to grind and be uniformly distributed up to iron, nitrogen, carbon
Metal organic frame polymer.
The equally distributed metal organic frame polymer of the iron, nitrogen, carbon of synthesis is transferred in porcelain boat by step 2, and is put into
It is calcined under an inert atmosphere in tube furnace, gas flow is 100 ml min-1Argon gas, first with 5 DEG C/min heating rate heating
To 200 DEG C, 1 hour is kept the temperature, then is warming up to 900 DEG C with 5 DEG C/min, keeps the temperature 2 hours, last Temperature fall is cooling up to for acid
The base metal elctro-catalyst MeIm-Cpur-1h-900 of property oxygen reduction reaction.
Embodiment 2
Step 1) weighs 2.658g(22.5mmol) benzimidazole, 0.518g(7.5mmol) 1,2,4- triazoles are added to and are equipped with
In the three-neck flask of 120ml methanol, ultrasonic 10min is to being uniformly dispersed.Weighing 2.9749g(10mmol) zinc nitrate hexahydrate is dissolved in
In 30ml methanol, 0.1352g(0.5mmol is weighed) it is dissolved in 1ml deionized water, until ultrasonic mixing is uniform.It is added to and is dissolved in nitre
In the methanol solution of sour zinc, ultrasonic mixing is uniformly distributed metallic solution, is added in three-neck flask, microwave reaction 1h.To anti-
It should terminate, filter, and washed with methanol and must precipitate three times.It is placed in baking oven to dry to take out to grind and be uniformly distributed up to iron, nitrogen, carbon
Metal organic frame polymer.
The equally distributed metal organic frame polymer of the iron, nitrogen, carbon of synthesis is transferred in porcelain boat by step 2, and is put into
It is calcined under an inert atmosphere in tube furnace, gas flow is 100 ml min-1Argon gas, first with 5 DEG C/min heating rate heating
To 200 DEG C, 1 hour is kept the temperature, then is warming up to 900 DEG C with 5 DEG C/min, keeps the temperature 2 hours, last Temperature fall is cooling up to for acid
The base metal elctro-catalyst BIZ-TAZ-1h-900 of property oxygen reduction reaction.
Comparative example 1
Step 1) weighs 1.8474g(22.5mmol) 2-methylimidazole, 1.1592g(7.5mmol) 6-chloropurine is added to and is equipped with
In the three-neck flask of 120ml methanol, ultrasonic 10min is to being uniformly dispersed.Weighing 2.9749g(10mmol) zinc nitrate hexahydrate is dissolved in
In 30ml methanol, 0.1352g(0.5mmol is weighed) it is dissolved in 1ml deionized water, until ultrasonic mixing is uniform.It is added to and is dissolved in nitre
In the methanol solution of sour zinc, ultrasonic mixing is uniformly distributed metallic solution, is added in three-neck flask, microwave reaction 2h.To anti-
It should terminate, filter, and washed with methanol and must precipitate three times.It is placed in baking oven to dry to take out to grind and be uniformly distributed up to iron, nitrogen, carbon
Metal organic frame polymer.
The equally distributed metal organic frame polymer of the iron, nitrogen, carbon of synthesis is transferred in porcelain boat by step 2, and is put into
It is calcined under an inert atmosphere in tube furnace, gas flow is 100 ml min-1Argon gas, first with 5 DEG C/min heating rate heating
To 200 DEG C, 1 hour is kept the temperature, then is warming up to 900 DEG C with 5 DEG C/min, keeps the temperature 2 hours, last Temperature fall is cooling up to for acid
The base metal elctro-catalyst MeIm-Cpur-2h-900 of property oxygen reduction reaction.
Comparative example 2
Step 1) weighs 1.8474g(22.5mmol) 2-methylimidazole, 1.1592g(7.5mmol) 6-chloropurine is added to and is equipped with
In the three-neck flask of 120ml methanol, ultrasonic 10min is to being uniformly dispersed.Weighing 2.9749g(10mmol) zinc nitrate hexahydrate is dissolved in
In 30ml methanol, 0.1352g(0.5mmol is weighed) ferric chloride hexahydrate is dissolved in 1ml methanol, until ultrasonic mixing is uniform.It is added
Into the methanol solution for being dissolved in zinc nitrate, ultrasonic mixing is uniformly distributed metallic solution, is added in three-neck flask, microwave reaction
1h.To the end of reacting, filter, and washed with methanol and must precipitate three times.Drying taking-up in baking oven is placed in grind up to iron, nitrogen, carbon
Equally distributed metal organic frame polymer.
The equally distributed metal organic frame polymer of the iron, nitrogen, carbon of synthesis is transferred in porcelain boat by step 2, and is put into
It is calcined under an inert atmosphere in tube furnace, gas flow is 100 ml min-1Argon gas, first with 5 DEG C/min heating rate heating
To 200 DEG C, 1 hour is kept the temperature, then is warming up to 1000 DEG C with 5 DEG C/min, keeps the temperature 2 hours, last Temperature fall cooling is used for obtain the final product
The base metal elctro-catalyst MeIm-Cpur-1h-1000 of acid oxygen reduction reaction.
Claims (9)
1. a kind of preparation process of the base metal elctro-catalyst with double ligand strategies for oxygen reduction reaction, synthesis process packet
Include following steps: step 1) directly synthesizes equally distributed metal organic frame polymer using two kinds of ligands and source metal, claims
A certain amount of two kinds of ligands are taken, are mixed and stirred for uniformly being scattered in it in solvent, a certain amount of two kinds of metal salts are added, wherein
Two kinds of metals are dissolved with solvent respectively, are added after being uniformly dispersed, and reaction a period of time, are washed with solvent, are filtered to obtain precipitating, are placed in
Iron obtained by drying, nitrogen, the equally distributed metal organic frame polymer of carbon, step 2 are uniform by the iron, nitrogen, carbon of synthesis in baking oven
The metal organic frame polymer of distribution is transferred in porcelain boat, and is put into tube furnace and is calcined certain time at a certain temperature,
The cooling base metal elctro-catalyst up to for acid oxygen reduction reaction of Temperature fall.
2. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: molysite described in step 1) can for Fe(NO3)39H2O, ferric chloride hexahydrate, six ferrous sulfate hydrate ammoniums, ferrous sulfate,
The one or two of ferric sulfate, Iron dichloride tetrahydrate, four hydration ferrous acetates, anhydrous frerrous chloride and anhydrous ferric chloride.
3. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: zinc salt described in step 1) can be the one or two of zinc nitrate hexahydrate, zinc sulfate, zinc chloride and zinc acetate.
4. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: the molar ratio of two kinds of ligands described in step 1) is 1:(1-5), two kinds of ligands can for 2-methylimidazole, benzimidazole,
Any two kinds in 1,2,4- triazole, 6-chloropurine.
5. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: disperse described in step 1) two kinds of ligands solvent can for methanol, ethyl alcohol, deionized water, N,N-dimethylformamide, N,
One or both of N- dimethyl acetamide.
6. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: the solvent of dispersed metal molysite described in step 1) and zinc salt can be methanol, ethyl alcohol, deionized water, N, N- dimethyl methyl
One or both of amide, DMAC N,N' dimethyl acetamide.
7. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: reaction a period of time can be 10-120min after being uniformly dispersed described in step 1).
8. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: solvent used can be methanol, ethyl alcohol, deionized water, N,N-dimethylformamide, N, N- when filtering described in step 1)
One or both of dimethyl acetamide.
9. the preparation method of the base metal elctro-catalyst according to claim 1 for oxygen reduction reaction, feature
Be: it can be argon gas or nitrogen that calcination process, which is logical inert gas, in high temperature process furnances described in step 2, and gas flow is
50-120ml/min, calcination process are warming up to 150-200 DEG C with the rate of 1-10 DEG C/min, keep the temperature 0.5-1.0 hours；Again with 1-
The rate of 5 DEG C/min is warming up to 800-1000 DEG C, keeps the temperature 1-3.0 hours.
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| CN111146457A (en) * | 2019-12-27 | 2020-05-12 | 大连理工大学 | Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound |
| CN113054205A (en) * | 2021-03-31 | 2021-06-29 | 哈尔滨工业大学 | Heat treatment process for improving oxygen reduction catalytic activity of non-noble metal catalyst |
| CN113529108A (en) * | 2021-07-27 | 2021-10-22 | 扬州大学 | For reducing CO2Preparation method and application of composite electrocatalyst |
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