CN107346826A - A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron - Google Patents
A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron Download PDFInfo
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- CN107346826A CN107346826A CN201710544117.XA CN201710544117A CN107346826A CN 107346826 A CN107346826 A CN 107346826A CN 201710544117 A CN201710544117 A CN 201710544117A CN 107346826 A CN107346826 A CN 107346826A
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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
- H01M4/9041—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
- 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
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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
A kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron, belongs to electro-catalysis technical field.Utilize the g C of cheap and rich nitrogen3N4For raw material, surfactant is added, source of iron, the scattered elctro-catalyst of monatomic iron has been obtained by high temperature pyrolysis.The catalyst has the features such as synthetic method is simple, pollution-free, and reactant is cheap and easy to get, and the catalyst prepared shows the chemical property suitable with platinum carbon in acidity, is with a wide range of applications.
Description
Technical field
The present invention is a kind of new preparation method of the oxygen reduction electro-catalyst disperseed on monatomic iron, belongs to electro-catalysis
Technical field.
Background technology
With a large amount of burnings of fossil fuel the significant problem of environmental degradation and energy shortage with discharge, facing mankind.
Therefore, find and develop the main task that a kind of green, environmental protection and the clean energy resource of sustainable development are current research workers.
Fuel cell is that a kind of generating that chemical energy is converted into electric energy by electrochemical reaction fills as a kind of new energy
Put, the oxidation reaction of hydrogen occurs in the anode of battery, the reduction reaction of oxygen occurs for negative electrode, and the whole of fuel cell reacted
Unique product is water in journey, does not bring any complicated side reaction and accessory substance, it have high conversion efficiency, it is pollution-free,
Noise is low and high reliability, receives the extensive concern of people recent years, especially most potential business now
The Proton Exchange Membrane Fuel Cells of change.Proton Exchange Membrane Fuel Cells will play an important role in the near future, its quilt
It is known as the ultimate power supply of electric automobile.
But fuel cell is also without commercialized reason up to now, either still occurs in anode in negative electrode
Chemical reaction is required for noble metal platinum otherwise to react the slow of progress so that the performance of battery is greatly attenuated as catalyst.According to system
Meter, 100kW fuel cell car about needs 100g Pt, and Pt reserves are only 39000t in the earth's crust.Platinum scarcity is led
Cause the cost of fuel cell car too high.And the reaction rate of cathodic oxygen reduction (ORR) is than anode hydroxide reaction (HOR)
The small several orders of magnitude of speed, so the oxygen reduction reaction on negative electrode is the key for researching and developing fuel cell.At present, base metal is developed
Catalyst replaces the research emphasis direction that noble metal platinum is fuel cell.Current research is roughly divided into both direction：First, grind
The relatively low catalyst of platinum content is made, such as platinum alloy structure, core shell structure；Second, replaced completely using base metal
Noble metal platinum, some nonmetallic or base metals are such as adulterated in carbon material.Exotic atom doping carbon material have cost it is low,
The excellent specific properties such as performance is good, methanol tolerance, anti-carbon monoxide, strong technology branch is provided for the commercialized development of fuel cell
Hold.Since Jasinski in 1964 has found that cobalt phthalocyanine can be catalyzed the reduction of oxygen in alkaline electrolyte, exotic atom doping
Carbon material develops rapidly in electrochemistry.As the continuous progress of research is with going deep into, exotic atom adulterates carbon material in alkalescence
Under the conditions of hydrogen reduction electrocatalysis characteristic can reach the level suitable with platinum carbon, and surpass in stability and methanol tolerance
Business platinum is crossed.
Fuel cell is generally divided into two kinds according to the difference of electrolyte：One kind is alkaline fuel cell, and one kind is acid
Fuel cell, Proton Exchange Membrane Fuel Cells is a kind of battery it is believed that most promising in acidic fuel cell,
Because the energy density of its offer of Proton Exchange Membrane Fuel Cells is alkaline fuel cell, lithium battery, methanol fuel cell
3-10 times or so, this kind of battery finally promises to be the first choice of later portable set.Although your non-gold under acid condition
Category oxygen reduction catalyst development be also rapidly, but sent from the performance of electrocatalytic oxidation reduction reaction see or with business
Platinum carbon has a certain distance, can be reached in the basic conditions especially for without metal-doped carbon-supported catalysts, this kind of catalyst
To the electro-catalysis ability suitable with platinum carbon, but performance in acid condition is very weak and extremely unstable, so development
It is us that a kind of catalyst either still can show excellent electrocatalysis characteristic in the basic conditions in acid condition
The emphasis to be studied.
The content of the invention
First technical problem to be solved by this invention is current situation and the electrochemistry key for fuel cell
A kind of preparation method of the scattered elctro-catalyst of brand-new monatomic iron is proposed in technical problem, this catalyst is either in acid
Still can reach in the basic conditions under the conditions of property with platinum carbon similar in hydrogen reduction performance.
Second technical problem to be solved by this invention is the presoma (g-C in nitrogen source carbon source3N4) in add molysite,
The higher nanoporous carbon of degree of graphitization is obtained by high temperature cabonization.
3rd technical problem to be solved by this invention is in (g-C3N4) and the composite of molysite in add anion
Surfactant F127, to cause etal molysite to be unlikely to reunite under high temperature pyrolysis, play a part of good dispersant, enter
And prepare the scattered elctro-catalyst of monatomic iron.
The present invention is in order to solve the above technical problems, used technical scheme is in carbon source nitrogen source (g-C3N4) in add table
Face activating agent F127 and a small amount of molysite, are carbonized in temperature programming tube furnace, by probing into etal molysite addition not
The electro-catalysis for not being all control variable, further preparing excellent performance that is same, whether adding surfactant, carburizing temperature
Agent.
The specific synthesis step of the present invention is as follows：
(1) a certain amount of presoma containing C, N is put into tube furnace and be carbonized, obtain presoma g-C3N4；
(2) by certain g-C3N4Ultrasonic disperse, magnetic agitation are dissolved in water；
(3) surfactant, magnetic agitation are added into step (2) solution；
(4) water-soluble molysite is added into the mixture obtained by step (3), is stirred, dries, is denoted as product 1；
(5) product 1 is put into the tube furnace high temperature carbonization of procedural heating, pickling, washes, dries, obtain monatomic iron
Scattered oxygen reduction electro-catalyst.
Penetrated by ESEM, transmission electron microscope, spherical aberration Electronic Speculum, synchrotron radiation, Raman spectrum, x-ray photoelectron power spectrum, X
A series of signs such as line difraction spectrum, inductivity coupled plasma mass spectrometry, organic element analysis, complete analysis demonstrate prepared
Material is the scattered metal of the monatomic iron of high dispersive, nitrogen co-doped porous carbon materials.
Further, the presoma containing C, N is selected from urea, cyanamide, dicyandiamide, melamine, thiocarbamide, three in step (1)
Attain cycle compound etc..The heating rate being carbonized in tube furnace is 2-10 DEG C/min, 500-600 DEG C of carburizing temperature, is carbonized and keeps
Time is 1-10 hours.The quality that presoma more than in step (1) is once carbonized is 0.01-20g.
Further, g-C in step (2)3N4With the water g-C that magnitude relation is every 0.01-5g3N4Corresponding water is 10-
100ml, the time of ultrasonic agitation is 0.5-10 hours.
Further, surfactant is added in step (3), surfactant is anion surfactant or nonionic
Surfactant, such as carboxylate, sulfuric acid, sulfonate and phosphate ester salt, F127 etc..g-C3N4With the matter of surfactant
Amount ratio is 0.01-100:1.
Further, add in step (4) molysite can be ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, iron chloride,
Frerrous chloride etc..The molysite and g-C of addition3N4Molar ratio be 0.01-10:1.
Further, before being heated up in step (5) to tube furnace, protective gas is first passed through as protection gas, during holding
Between 1-3 hours, protective gas may be selected from nitrogen, argon gas, helium, neon, Krypton, xenon or radon gas etc..The heating of carbonisation
Speed is 0.5-30 DEG C/min.The temperature of carbonization is 500-1200 DEG C (preferably 800-1000 DEG C), is incubated 0.5- at such a temperature
8h, naturally cool to room temperature.
The acid of pickling may be selected from nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid etc. in step (5).
From urea as preparation g-C in preferred steps (1)3N4Presoma, nitrogen protect gas under with 3 DEG C per minute
Heating, kept for 2 hours at 550 DEG C, preferably per 0.3g g-C in step (2)3N4, add 30ml water and 2 hours be stirred by ultrasonic,
Polyethers F127 is preferably used in step (3) anion surfactant, with g-C3N4Mass ratio be preferably used 1:1, step
(4) FeCl is preferably used in3As molysite, with g-C3N4Molar ratio be preferably used 0.1:1.In step (5) preferably
Nitrogen 2 hours retention times, is risen with 2 DEG C per minute of speed, kept for 2 hours at 800 DEG C as protection gas.Pickling is preferential
Hydrochloric acid is selected on ground.
Beneficial effects of the present invention are as follows：
1) with cheap g-C3N4As presoma, surfactant and a small amount of etal molysite are added wherein, are passed through
One step is pyrolyzed to have obtained the porous C catalyst of the monatomic Fe2O3 doping of high degree of dispersion, and the catalyst is greatly less than in price
Noble metal platinum carbon, the hydrogen reduction electrocatalysis characteristic of this catalyst can be with either in acid condition or under alkalescence condition
Reach the degree compared with business platinum carbon, and stability will be better than business platinum performance with methanol tolerance, this catalyst
The platinum carbon instead of business will be hopeful, and then make it that the pem cell of acidity is commercialized, be electro-catalysis
Development provides some basic researchs, has wide practical use in terms of electrocatalytic oxidation reduction.
2) compared with prior art, this method preparation process is simple, easy to operate.G-C after the carbonization of the present invention3N4Become
Into the structure for being similar to graphene platelet, iron is uniformly dispersed in porous carbon materials in the form of monoatomic；Porous carbon
Material is more beneficial for passing with excellent electric conductivity, high-specific surface area and the grade pore structure coexisted with micropore, mesoporous and macropore
The transmission of matter and electric charge.The porous carbon of transition metal Fe2O3 doping provides substantial amounts of avtive spot, and the electricity for promoting catalyst is urged
Change performance.
3) preparation process of the present invention is avoided using toxic reagent and complicated synthesis technique, and preparation process is simple, operation
It is convenient, easily realize large-scale production.
4) present invention uses urea, molysite as presoma, is conveniently easy to get, so that the cost of catalyst substantially reduces.
Brief description of the drawings
Fig. 1 is to use g-C in embodiment 13N4The method schematic diagram of the scattered elctro-catalyst of monatomic iron is prepared for raw material.
Fig. 2 is the electron scanning micrograph of the catalyst that monatomic iron is scattered in embodiment 1.
Fig. 3 is the transmission electron microscope photo of the catalyst that monatomic iron is scattered in embodiment 1.
(Fig. 4 can not use colour to the distribution diagram of element for the catalyst that Fig. 4 disperses for monatomic iron in embodiment 1, please be changed to black
In vain, it is also unclear, unnecessary to be deleted).
Fig. 5 is the X-ray diffraction spectra of the catalyst that monatomic iron is scattered in embodiment 1.
Fig. 6 be monatomic iron is scattered in embodiment 1 catalyst and business Pt/C hydrogen reduction be catalyzed LSV comparison diagrams (
Alkaline 0.1M potassium hydroxide).
Fig. 7 is that the hydrogen reduction of the scattered catalyst and business Pt/C of the monatomic iron in embodiment 1 is catalyzed LSV comparison diagrams
(in acid 0.5M sulfuric acid).
Fig. 8 is the transmission electron microscope photo that iron nano-particle adulterates porous C catalyst in comparative example 2.
Fig. 9 is the transmission electron microscope photo that iron nano-particle adulterates porous C catalyst in embodiment 3.
Figure 10 be in comparative example 2 iron nano-particle adulterate porous carbon and business Pt/C hydrogen reduction be catalyzed LSV comparison diagrams (
Alkaline 0.1M potassium hydroxide).
Figure 11 be in embodiment 3 iron nano-particle adulterate porous carbon and business Pt/C hydrogen reduction be catalyzed LSV comparison diagrams (
Alkaline 0.1M potassium hydroxide).
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the present invention is not limited to following reality
Apply example.
Experimental drug from business it is regular sale (An Naiji, Chinese medicines group, Beijing Chemical Plant, Du Pont, J＆K,
Alfar), do not purify further unless otherwise indicated.
Embodiment 1：With g-C3N4The method that the scattered elctro-catalyst of monatomic iron is prepared for raw material
1) 3g urea is weighed, is put into tube furnace and is heated up with 3 DEG C per minute of programming rate, 550 DEG C of 2 hours of holding,
Automatic cooling.
2) the product g-C synthesized in 0.3g steps (1) is weighed3N4, add 30ml deionized water, ultrasonic half an hour,
Stir 1.5 hours.
3) 0.3g polyethers F127 will be added in the product of step (2), stirs 2 hours.
4) 1ml, 0.298M FeCl will be added in the solution of step (3)3Solution, 8 hours are stirred, in the stirring of heating
Be warming up in device 100 DEG C naturally stirring air-dry.
5) above-mentioned dried powder, which is put into tube furnace, is carbonized, and temperature is raised to 800 DEG C (with 2 DEG C per minute of speed
Rise, 800 DEG C of 2 hours of holding), the product after carbonization is taken out, soaked 12 hours with 1MHCl 5ml, filtering, with substantial amounts of
Water rinses, and untill PH=7, is denoted as SA-Fe/NG.
Comparative example 2：With g-C3N4The method that nano particle Fe-Mn cycle and transference carbon elctro-catalyst is prepared for raw material
1) 3g urea is weighed, is put into tube furnace and is heated up with 3 DEG C per minute of programming rate, 550 DEG C of 2 hours of holding,
Automatic cooling.
2) the product g-C3N4 synthesized in 0.3g steps (1) is weighed, adds 30ml deionized water, ultrasound is small half
When, stir 1.5 hours.
3) 1ml will be added in the solution of step (2), 0.298M FeCl3 solution, 8 hours are stirred, in the stirring of heating
Be warming up in device 100 DEG C naturally stirring air-dry.
4) above-mentioned dried powder, which is put into tube furnace, is carbonized, and temperature is raised to 800 DEG C (with 2 DEG C per minute of speed
Rise, 800 DEG C of 2 hours of holding), the product after carbonization is taken out, soaked 12 hours with 1MHCl 5ml, filtering, with substantial amounts of
Water rinses, and untill PH=7, is denoted as Fe/NG.
Embodiment 3：With g-C3N4The method that nano particle Fe-Mn cycle and transference carbon elctro-catalyst is prepared for raw material
1) 3g urea is weighed, is put into tube furnace and is heated up with 3 DEG C per minute of programming rate, 550 DEG C of 2 hours of holding,
Automatic cooling.
2) the product g-C synthesized in 0.3g steps (1) is weighed3N4, add 30ml deionized water, ultrasonic half an hour,
Stir 1.5 hours.
3) 0.3g polyethers F127 will be added in the product of step (2), stirs 2 hours.
4) 5ml, 0.298M FeCl will be added in the solution of step (3)3Solution, 8 hours are stirred, in the stirring of heating
Be warming up in device 100 DEG C naturally stirring air-dry.
5) above-mentioned dried powder, which is put into tube furnace, is carbonized, and temperature is raised to 800 DEG C (with 2 DEG C per minute of speed
Rise, 800 DEG C of 2 hours of holding), the product after carbonization is taken out, soaked 12 hours with 1MHCl 5ml, filtering, with substantial amounts of
Water rinses, and untill PH=7, is denoted as Fe/NG-1.
Above-described embodiment is only intended to clearly illustrate example of the present invention, and is not the embodiment party to the present invention
The restriction of formula, for those of ordinary skill in the field, other differences can also be made on the basis of the above description
The change or variation of form, all embodiments can not be exhaustive here, it is every to belong to technical scheme institute
Row of the obvious changes or variations extended out still in protection scope of the present invention.
Fig. 2 is the stereoscan photograph of the catalyst that monatomic iron is scattered after embodiment 1 is carbonized, and is as can be seen from the figure existed
G-C after carbonization3N4Become the structure similar to graphene platelet, and without the aggregation of discovery iron particle, this and Fig. 3
The photo of transmission electron microscope be consistent.
Fig. 4 is the spherical aberration electron microscope of the catalyst that monatomic iron is scattered after embodiment 1 is carbonized, by overall diagram it can be seen that not
In the presence of the particle of big iron, but a large amount of dots are found under 10nm high powers, prove that these dots are iron by elementary analysis, this
Illustrating that iron is uniformly dispersed in porous carbon materials in the form of monoatomic so that the active sites of the catalyst largely expose,
Therefore catalytic performance improves.
Claims (10)
1. the preparation method of the scattered oxygen reduction electro-catalyst of a kind of monatomic iron, it is characterised in that comprise the following steps：
(1) a certain amount of presoma containing C, N is put into tube furnace and be carbonized, obtain presoma g-C3N4；
(2) by certain g-C3N4Ultrasonic disperse, magnetic agitation are dissolved in water；
(3) surfactant, magnetic agitation are added into step (2) solution；
(4) water-soluble molysite is added into the mixture obtained by step (3), is stirred, dries, is denoted as product 1；
(5) product 1 is put into the tube furnace high temperature carbonization of procedural heating, pickling, washes, dries, obtain monatomic iron and disperse
Oxygen reduction electro-catalyst.
2. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In the presoma containing C, N attains cycle compound selected from urea, cyanamide, dicyandiamide, melamine, thiocarbamide, three in step (1).
The heating rate that step (1) is carbonized in tube furnace is 2-10 DEG C/min, 500-600 DEG C of carburizing temperature, and the carbonization retention time is
1-10 hours.
3. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In g-C in step (2)3N4With the water g-C that magnitude relation is every 0.01-5g3N4Corresponding water is 10-100ml；Step (2)
The time of middle ultrasonic agitation is 0.5-10 hours.
4. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In addition surfactant in step (3) in step (2), surfactant is anion surfactant or nonionic table
Face activating agent；g-C3N4Mass ratio with surfactant is 0.01-100:1.
5. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In surfactant is selected from carboxylate, sulfuric acid, sulfonate and phosphate ester salt, F127 in step (2).
6. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In the molysite and g-C of addition3N4Molar ratio be 0.01-10:1.
7. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In addition molysite is selected from ferric sulfate, ferrous sulfate, ferric nitrate, ferrous nitrate, iron chloride, frerrous chloride in step (4).
8. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In before being heated up in step (5) to tube furnace, being first passed through protective gas, hour retention time 1-3；The liter of carbonisation
Warm speed is 0.5-30 DEG C/min, and the temperature of carbonization is 500-1200 DEG C (preferably 800-1000 DEG C), is incubated at such a temperature
0.5-8h, naturally cool to room temperature.
9. according to a kind of preparation method of the scattered oxygen reduction electro-catalyst of monatomic iron described in claim 1, its feature exists
In from urea as preparation g-C in step (1)3N4Presoma, nitrogen protect gas under with 3 DEG C per minute heating, 550
DEG C kept for 2 hours, preferably per 0.3g g-C in step (2)3N4, add 30ml water and be stirred by ultrasonic 2 hours, step (3) it is cloudy from
Polyethers F127 is preferably used in sub- surfactant, with g-C3N4Mass ratio be preferably used 1:1, in step (4) preferably
Use FeCl3As molysite, with g-C3N4Molar ratio be preferably used 0.1:1；Preferably nitrogen is as guarantor in step (5)
Gas is protected, 2 hours retention times, is risen with 2 DEG C per minute of speed, is kept for 2 hours at 800 DEG C.Hydrochloric acid is preferentially selected in pickling.
10. the scattered oxygen reduction electro-catalyst of the monatomic iron being prepared according to any one of claim 1-9 preparation method.
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| CN108246330A (en) * | 2018-01-12 | 2018-07-06 | 北京化工大学 | A kind of method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling |
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| CN114275777A (en) * | 2021-12-28 | 2022-04-05 | 盐城工学院 | Preparation method of high-graphitization-degree carbon-based material for lithium battery negative electrode |
| CN115954491A (en) * | 2022-12-01 | 2023-04-11 | 中南大学 | Preparation method of nitrogen-doped functionalized carbon-supported platinum transition metal binary ordered alloy catalyst |
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