CN106252673A - A kind of preparation method of Fe N/C oxygen reduction reaction catalyst based on natural plants tissue - Google Patents
A kind of preparation method of Fe N/C oxygen reduction reaction catalyst based on natural plants tissue Download PDFInfo
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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
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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
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Abstract
The present invention discloses the preparation method of a kind of Fe N/C oxygen reduction reaction catalyst based on natural plants tissue, it is by after the pulverizing of natural plants tissue, hydrothermal carbonization, low-temperature freeze drying, carrying out high-temperature roasting in 700～1000 DEG C under an inert atmosphere, products therefrom adulterates with source of iron, low-temperature freeze drying again, high-temperature roasting, prepares the porous carbon materials oxygen reduction catalyst of ferrum N doping by above step.The performance of this catalyst catalytic oxygen reduction reaction in the basic conditions is suitable with 20%Pt/C catalyst, but cost is but less than platinum based catalyst, can be widely applied to fuel cell and metal-air battery manufactures field.
Description
Technical field
The present invention relates to the preparation method of a kind of Fe-N/C oxygen reduction reaction catalyst based on natural plants tissue,
Belong to electrocatalysis material preparation field.
Background technology
In the face of the energy crisis of globalization, the new energy materials pursuing clean and effective becomes people's exigence.By
Reaction in fuel in a fuel cell and oxygen not by a process burnt but passes through a gentle electrification
The process learned, its transformation efficiency is not limited by Carnot law, has efficient and reusable feature, and fuel cell becomes
Increasingly has a potential energy conversion devices.But, multielectron transfer process, slowly dynamic process, higher mistake
Electromotive force governs the efficiency of fuel battery negative pole redox reactions.Therefore improve the efficiency of redox reactions on negative electrode, seek
Look for efficient oxygen reduction catalyst imperative.
At present, the more commonly used oxygen reduction catalyst be material with carbon element be the platinum based catalyst of carrier, but platinum based catalyst
Having cost high, unstable, methanol tolerance poisons the shortcomings such as ability, seriously constrains its large-scale application.Therefore find
A kind of low platinum content or non-precious metal catalyst will have the biggest application prospect.At present, nitrogenous carbon-supported transitional metal (Fe,
Co etc.) catalyst has the good stability of higher hydrogen reduction catalytic effect and methanol tolerance poisons effect has wide work
Industry application prospect.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to be to provide a kind of Fe-N/C based on natural plants tissue
The preparation method of oxygen reduction reaction catalyst.This catalyst has higher hydrogen reduction catalytic performance, and good stability is with anti-
Methanol poisons effect and low cost, and preparation method simply can be widely applied to large-scale production.
In order to realize above-mentioned technical purpose, the invention provides the preparation side of a kind of Fe-N/C oxygen reduction reaction catalyst
Method, comprises the following steps:
(1), after natural plants tissue being pulverized, it is mixed in reactor with distilled water, hydrothermal carbonization, after lyophilization,
It is placed in nitrogen atmosphere, high-temperature roasting, obtains the material with carbon element of N doping；
(2) material with carbon element of step (1) gained N doping is fully mixed with iron salt, distilled water, stirring, lyophilization, nitrogen
Gas atmosphere at high temperature roasting.
In said method, in the water heating kettle of step (1), natural plants tissue and mass ratio≤1/10 of water.
Wherein the condition of step (1) hydrothermal carbonization is: temperature 120～250 DEG C, the time 8～16h.
Preferably, the temperature of hydrothermal carbonization is 180 DEG C.
Preferably, the natural plants tissue described in step (1) selected from Folium Mori, corn cob, Herba Taraxaci and Radix Artemisia ordosicae at least one.
The lyophilization condition of step (1) and step (2) is temperature-10 DEG C～-50 DEG C, and the time is 8～12h.
Preferably, cryodesiccated temperature is-50 DEG C.
Preferably, the lyophilization of step (1) and step (2) is to carry out in vacuum refrigerating machine.
It is 700～1000 DEG C that step (1) and step (2) high-temperature roasting condition are temperature, and the time is 1～3h.
Preferably, high-temperature roasting condition be 800-900 DEG C.
Iron salt described in step (2) is at least one in iron chloride, iron sulfate, ferric nitrate.
Mass ratio≤1/50 of the material with carbon element of described iron salt and N doping.
Mass ratio≤1/40 of the material with carbon element of described distilled water and N doping.
Step (1) and the high-temperature roasting stage of step (2), heating rate is 2～5 DEG C/min.
The invention provides the catalyst that said method prepares.
The catalyst that the said method of the present invention prepares, it includes C, N, O and Fe element；Wherein, the matter of each element
Amount degree is: C 50%～80%, N 1%～4%, O 15%～35%, Fe 4%～7%.
Present invention also offers the application in battery manufacture of the above-mentioned catalyst.
Described battery is fuel cell or metal-air battery.
Preferably scheme, the Fe-N/C oxygen reduction reaction catalyst of preparation includes C, N, O and Fe element；Wherein, each element
Mass percentage content be: C 50～80%, N 1～4%, O 15～35%, Fe 4～7%.
Hinge structure, the Advantageous Effects that technical scheme is brought:
1, the preparation method of the present invention utilizes natural plants to be organized as raw material, pollution-free, low cost, and preparation is simple, bar
Part is easily-controllable, be expected to industrialized large-scale production；And overcome existing nitrogenous carbon-supported transitional metal (Fe, Co etc.) catalyst
Complicated process of preparation, the shortcoming such as condition is harsh.
2, in the Fe-N/C oxygen reduction reaction composite catalyst preparation process of the present invention, freeze-drying method is used, favorably
Produce loose structure in catalyst, increase specific surface area and mass-transfer efficiency, promote the lifting of oxygen reduction performance.
3, the Fe-N/C oxygen reduction reaction catalyst that prepared by the present invention has high oxygen reduction catalytic activity in alkaline medium,
Its stability and methanol tolerance poison ability and are better than 20%Pt/C, are expected to substitute traditional Pt noble metal catalyst.
Accompanying drawing explanation
The Fe-N/C oxygen reduction reaction catalyst sample that in Fig. 1, embodiment 1 prepares is electrolysed at the 0.1M KOH that oxygen is saturated
Oxygen reduction reaction cyclic voltammogram in liquid.
Fig. 2 be A, B two figure be the SEM of the Fe-N/C oxygen reduction reaction catalyst that embodiment 2 prepares under different amplification
Shape appearance figure, its pattern is the nano-carbon material of porous.
Fig. 3 is that the Fe-N/C oxygen reduction reaction catalyst sample that embodiment 2 prepares is electrolysed at the 0.1M KOH that oxygen is saturated
Oxygen reduction reaction cyclic voltammogram in liquid.
Fig. 4 is the catalyst sample EDX elementary analysis figure that embodiment 2 prepares.
Fig. 5 is the Fe-N/C oxygen former catalysts sample for preparing of embodiment 3 at the saturated 0.1M KOH electrolyte of oxygen
In oxygen reduction reaction cyclic voltammogram.
Fig. 6 is that the Fe-N/C oxygen reduction reaction catalyst sample that embodiment 2 prepares is electrolysed at the 0.1M KOH that oxygen is saturated
Oxygen reduction reaction rotating ring disk electrode (r.r.d.e) polarization curve in liquid.
Fig. 7 is that the 20%Pt/C catalyst of the prepared Fe-N/C catalyst sample of embodiment 2 and comparative example is at oxygen
Chronoamperogram in saturated 0.1M KOH+0.3M methanol electrolysis liquid.
Fig. 8 is that the 20%Pt/C catalyst of the catalyst sample for preparing of embodiment 2 and comparative example is satisfied at oxygen
Oxygen reduction reaction chrono-amperometric comparison diagram in the 0.1M KOH electrolyte of sum.
Fig. 9 is that the Fe-N/C oxygen reduction reaction catalyst sample that embodiment 7～9 prepares is electric at the 0.1M KOH that oxygen is saturated
Solve the oxygen reduction reaction cyclic voltammogram in liquid.
Detailed description of the invention
Unless otherwise defined, the implication that all technical term used hereinafter is generally understood that with those skilled in the art
Identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the present invention
Protection domain.
Except there being special instruction, the various reagent used in the present invention, raw material be can commodity commercially or
The product that person can be prepared by known method.
The preparation (1) of embodiment 1 Fe-N/C catalyst
Folium Mori 10g after pulverizing adds deionized water 60mL in the hydrothermal reaction kettle of 100mL, reacts 10h at 180 DEG C,
At temperature is-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, it is warming up to 800 with 4 DEG C/min
DEG C heat treatment 2h, products therefrom is the material of N doping.
The material with carbon element of the 150mg N doping of gained is added 10mL deionized water, 3mg FeCl312h, temperature is stirred under room temperature
For lyophilization 12h again at-50 DEG C, under the protection of nitrogen atmosphere, it is warming up to 800 DEG C of heat treatment 2h with 4 DEG C/min, obtains
Fe-N/C catalyst.See Fig. 1.
The preparation (2) of embodiment 2 Fe-N/C catalyst
Folium Mori 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
For at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, products therefrom is the material of N doping.
The material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 3mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.The SEM shape appearance figure of catalyst sample is shown in Fig. 2, the oxygen reduction cyclic voltammetric of catalyst sample
Figure is shown in Fig. 3, and the EDX elementary analysis figure of catalyst sample is shown in Fig. 4.
Table 1 Fe-N-C-850 constituent content
The preparation (3) of embodiment 3 Fe-N/C catalyst
Folium Mori 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
For at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up at 900 DEG C of heat with 4 DEG C/min
Reason 2h, products therefrom is the material of N doping.
The material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 3mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 900 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The preparation (4) of embodiment 4 Fe-N/C catalyst
Folium Mori 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
For at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up at 800 DEG C of heat with 4 DEG C/min
Reason 2h, products therefrom is the material of N doping
The material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 2mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 800 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The preparation (5) of embodiment 5 Fe-N/C catalyst
Folium Mori 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
For at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, products therefrom is the material of N doping
The material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 2mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The preparation (6) of embodiment 6 Fe-N/C catalyst
Folium Mori 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
For at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up at 900 DEG C of heat with 4 DEG C/min
Reason 2h, products therefrom is the material of N doping
2): the material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 2mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 900 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The preparation (7) of embodiment 7 Fe-N/C catalyst
Corn cob 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
Degree at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up to 850 DEG C of heat with 4 DEG C/min
Processing 2h, products therefrom is the material of N doping
2): the material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 3mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The preparation (8) of embodiment 8 Fe-N/C catalyst
Herba Taraxaci 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
Degree at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up to 850 DEG C of heat with 4 DEG C/min
Processing 2h, products therefrom is the material of N doping
2): the material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 3mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The preparation (9) of embodiment 9 Fe-N/C catalyst
Folium Artemisiae Argyi 10g after pulverizing adds deionized water 60mL in the reactor of 100mL, reacts 10h, temperature at 180 DEG C
For at-50 DEG C after lyophilizing 12h in vacuum freeze-drying machine, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, products therefrom is the material of N doping
2): the material with carbon element of the 150mg N doping of step 1 gained is added 10mL deionized water, 3mg FeCl3Stir under room temperature
12h, temperature be-50 DEG C at lyophilization 12h again, under the protection of nitrogen atmosphere, be warming up at 850 DEG C of heat with 4 DEG C/min
Reason 2h, obtains Fe-N/C catalyst.
The Fe-N/C catalyst that embodiment 10 present invention prepares is right with 20%Pt/C commercial catalyst (Alfa Aesar)
Ratio.
The Fe-N/C catalyst sample that embodiment 1～3 prepares oxygen in the saturated 0.1M KOH electrolyte of oxygen
Reduction reaction cyclic voltammogram is shown in Fig. 1,3,5.When temperature is 800 DEG C, the take-off potential of Fe-N/C catalyst is-0.05V, temperature
When being 900 DEG C, the take-off potential of Fe-N/C catalyst is-0.1V, however the take-off potential of Fe-N/C that temperature is 850 DEG C be-
0.04V, has shuffled 0.01V and 0.06V respectively than the take-off potential of the Fe-N/C catalyst at a temperature of the first two.At 800 DEG C
The reduction peak current potential of the hydrogen reduction of Fe-N/C is-0.22V, the reduction peak current potential of the hydrogen reduction of the Fe-N/C at 900 DEG C is-
0.27V, and the reduction peak current potential of the hydrogen reduction of the Fe-N/C of 850 DEG C is-0.18V, is catalyzed than the Fe-N/C at a temperature of the first two
The reduction potential of agent has been shuffled 0.04V and 0.08V respectively, it can be seen that the Fe-N/C at 850 DEG C compares the first two temperature, and oxygen is also
Originality can have greatly improved.
The Fe-N/C catalyst sample of embodiment 2 preparation oxygen reduction reaction in the saturated 0.1M KOH electrolyte of oxygen
Rotating ring disk electrode (r.r.d.e) polarization curve, the electron transfer number having figure to understand Fe-N/C catalyst is 3.8, and hydrogen peroxide yield is
9%, it is the oxygen reduction process of 4 close electronics, sees Fig. 6.
The Fe-N/C catalyst sample of embodiment 2 preparation and 20%Pt/C are in the saturated 0.1M KOH electrolyte of oxygen
Methanol poisons experiment, and the methanol solution that chrono-amperometric technology adds 3M in system when 300s is taked in this experiment.Experiment preparation
Fe-N/C catalyst compare 20%Pt/C catalyst there is the effect that more preferable methanol tolerance poisons.Result is shown in Fig. 7.
In the Fe-N/C catalyst sample of embodiment 2 preparation and the saturated 0.1M KOH electrolyte of 20%Pt/C oxygen
Stability experiment.By the Fe-N/C catalyst sample of chrono-amperometric commercial measurement embodiment 2 preparation and stablizing of 20%Pt/C
Property, after 3000s, the Opposed Current of 20%Pt/C catalyst have dropped 36%, and Fe-N/C catalyst Opposed Current have dropped
22%, the Fe-N/C catalyst of experiment preparation is compared 20%Pt/C Pt/C catalyst and is had more preferable stability.Result is shown in Fig. 8.
The oxygen reduction reaction cyclic voltammogram of the Fe-N/C catalyst sample of embodiment 7～9 preparation, is shown in Fig. 9.
Above embodiment is only to be described the preferred embodiment of the present invention, not enters the scope of the present invention
Row limits, on the premise of designing spirit without departing from the present invention, and this area ordinary skill technical staff technical side to the present invention
Various modification that case is made and improvement, all should fall in the protection domain that claims of the present invention determines.
Claims (10)
1. the preparation method of a Fe-N/C oxygen reduction reaction catalyst based on natural plants tissue, it is characterised in that include
Following steps:
(1), after natural plants tissue being pulverized, it is mixed in reactor with distilled water, hydrothermal carbonization, after lyophilization, is placed in
In nitrogen atmosphere, high-temperature roasting, obtain the material with carbon element of N doping；
(2) material with carbon element of step (1) gained N doping is fully mixed with iron salt, distilled water, stirring, lyophilization, nitrogen gas
High-temperature roasting under atmosphere.
Preparation method the most according to claim 1, it is characterised in that: in the water heating kettle of step (1), natural plants tissue with
Mass ratio≤1/10 of water.
Preparation method the most according to claim 1, it is characterised in that: the condition of step (1) hydrothermal carbonization is: temperature 120
～250 DEG C, the time 8～16h.
Preparation method the most according to claim 1, it is characterised in that: the lyophilization condition of step (1) and step (2) is equal
For temperature-10 DEG C～-50 DEG C, the time is 8～12h.
Preparation method the most according to claim 1, it is characterised in that: step (1) and step (2) high-temperature roasting condition are
Temperature is 700～1000 DEG C, and the time is 1～3h.
Preparation method the most according to claim 1, it is characterised in that: the iron salt described in step (2) is iron chloride, sulphuric acid
In ferrum, ferric nitrate at least one.
Preparation method the most according to claim 1, it is characterised in that: the quality of the material with carbon element of described iron salt and N doping
Mass ratio≤1/40 of the material with carbon element of ratio≤1/50, described distilled water and N doping.
Preparation method the most according to claim 1, it is characterised in that: step (1) and the high-temperature roasting stage of step (2),
Heating rate is 2～5 DEG C/min.
9. the catalyst prepared according to the preparation method described in any one of claim 1～8.
10. according to the catalyst described in claim, it is characterised in that: this catalyst includes C, N, O and Fe element；Wherein, respectively
The mass percentage content of element is: C 50%～80%, N 1%～4%, O 15%～35%, Fe 4%～7%.
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| CN109004241B (en) * | 2018-08-09 | 2021-05-14 | 南京大学连云港高新技术研究院 | Preparation method of iron-nitrogen-graphite carbon material |
| CN109560288A (en) * | 2018-11-29 | 2019-04-02 | 济南大学 | A kind of highly reactive form of oxygen reducing catalyst and preparation method and purposes |
| CN109560288B (en) * | 2018-11-29 | 2022-03-18 | 济南大学 | High-activity oxygen reduction catalyst, preparation method and application |
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