CN103551152A - Carbon-based non-noble metal oxygen reduction catalyst - Google Patents
Carbon-based non-noble metal oxygen reduction catalyst Download PDFInfo
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- CN103551152A CN103551152A CN201310509306.5A CN201310509306A CN103551152A CN 103551152 A CN103551152 A CN 103551152A CN 201310509306 A CN201310509306 A CN 201310509306A CN 103551152 A CN103551152 A CN 103551152A
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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
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- 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 discloses a carbon-based non-noble metal oxygen reduction catalyst, which aims to solve the problems that the existing organic metal macrocyclic-complex-type oxygen reduction catalyst is complicated in preparation process, harsh in reaction condition, low in yield and high in production cost, and has the poor catalytic activity and stability as compared with a noble metal catalyst taking platinum as a main component. A method for preparing the carbon-based non-noble metal oxygen reduction catalyst comprises the following steps: adding acetylene black into a reaction liquid, stirring and drying so as to obtain a precursor; and transferring the precursor into a tube furnace for heating. The cost of raw materials is low due to the fact that cobalt chloride, ammonia gas, the acetylene black and absolute ethyl alcohol are taken as the raw materials, so that the prepared catalyst is low in production cost. The method is simple to operate, convenient in production and small in equipment investment, thereby meeting the demands of actual production. Thus, the method is suitable for industrial mass production. In addition, the experimental result proves that the catalyst disclosed by the invention has good oxygen catalytic reduction activity and good stability.
Description
Technical field
The present invention relates to materials chemistry field, especially fuel-cell catalyst field, is specially a kind of carbon back non noble metal oxygen reduction catalyst.
Background technology
Proton Exchange Membrane Fuel Cells, is called for short PEMFC, and tool has the following advantages: 1) PEMFC energy density is high, and battery efficiency is high; 2) its electrolyte is solid, has effectively avoided the corrosion to battery material; 3) it can at room temperature move, and maximum operating temperature is 100 ℃ of left and right only, and operating temperature is low, can adapt to the needs of actual production; 4) it can start at normal temperatures, has and starts advantage efficiently; 5) it is environmentally friendly, can reduce the pollution to environment, for example, using hydrogen as fuel, and corresponding product is water, environmentally safe.Because Proton Exchange Membrane Fuel Cells has above-mentioned plurality of advantages, thereby be considered to the optimal power supply of mobile power (such as electric automobile etc.), attract widespread attention.
Yet from the sixties in 20th century, since Proton Exchange Membrane Fuel Cells is born, the commercialization but not obtaining is truly promoted, one of them main cause is that the cathodic reduction reaction due to oxygen in PEMFC has delay of response, the various feature of reaction path.In order to guarantee carrying out smoothly of reaction, oxygen reduction reaction need to carry out under catalyst action.
At present, well behaved oxygen reduction catalyst is mainly to take platinum as main noble metal catalyst.It is estimated, in fuel cell generation, the cost of pile accounts for 50%, and noble metal catalyst occupy the more than 50% of pile cost (list of references: Gang Wu, Karren L. More, Christina M. Johnston, Piotr Zelenay,
science, 2011,332:443-447), and platinum is as a kind of noble metal, and it is expensive, thereby adopts noble metal catalyst to make the cost of fuel cell be difficult to reduce, and has finally limited the large-scale commercial application of Proton Exchange Membrane Fuel Cells.Therefore, exploitation has the non noble metal oxygen reduction catalyst of the advantages such as cheap, catalytic activity good, good stability, resistance to methyl alcohol, for the development of Proton Exchange Membrane Fuel Cells, has crucial meaning.
From Jasinski in reported first in 1964 Cobalt Phthalocyanine since reaction has catalytic activity to fuel cell oxygen reduction (list of references R. Jasinski,
nature, 1964,201:1212-1213), the organic metal macrocyclic complex type oxygen reduction catalyst of similar porphyrin, phthalocyanine and derivative thereof is considered to most possible replacement and take platinum as main noble metal catalyst.The typical preparation method of this class catalyst is: certain transition metal ions (as Co, Fe ion etc.) is reacted and generates complex under long-time counterflow condition with containing n-donor ligand (as porphyrin, phthalocyanine); and be deposited on carbon black carrier; then under inert gas shielding; heat-treat, thereby prepare final catalyst.Chinese patent CN101069857A discloses a kind of halogen-substituted binuclear phthalocyanine ferrite reduction catacolyst, and the disclosed a kind of compound non noble metal oxygen reduction catalyst of Chinese patent CN101417242A, has all adopted these class methods.Yet also there is certain shortcoming in the method, as: its preparation process is complicated, severe reaction conditions, productive rate is lower, and the macrocyclic compound such as porphyrin, phthalocyanine is expensive, cause production cost still higher, simultaneously the catalytic activity, stability of the catalyst of preparation also with take platinum and have a certain distance as main noble metal catalyst.
To sum up, the discovery of organic metal macrocyclic complex type oxygen reduction catalyst has facilitation for the development of fuel cell, but appoint, so need to be further improved such catalyst.
Summary of the invention
Goal of the invention of the present invention is: the preparation process existing for existing organic metal macrocyclic complex type oxygen reduction catalyst is complicated, severe reaction conditions, productive rate is lower, production cost is still higher, catalytic activity, stability be take platinum as the main poor problem of noble metal catalyst, and a kind of carbon back non noble metal oxygen reduction catalyst is provided.It is raw material that cobalt chloride, ammonia, acetylene black, absolute ethyl alcohol are take in the present invention, and cost of material is low, thereby prepared Catalyst Production cost is low, and method of the present invention is simple to operate, convenient for production, and equipment investment is little, can meet the needs of actual production, be suitable for the needs that large-scale industrialization is produced.Meanwhile, experimental result shows that catalyst of the present invention has good oxygen catalytic reduction activity, good stability.
To achieve these goals, the present invention adopts following technical scheme:
A non noble metal oxygen reduction catalyst, is characterized in that, adopts the method comprising the steps to be prepared from:
The first step: cobalt chloride is dissolved in absolute ethyl alcohol, is prepared into reactant liquor;
Second step: acetylene black is joined in reactant liquor, mix, stir 20-60min, then, under the vacuum condition of 30-80 ℃, dry 1-10h, obtains presoma;
The 3rd step: presoma is transferred in tube furnace, first pass into ammonia 10-30min, the flow of ammonia is 20-500mL/min, then keep ammonia flow constant, to heating up in tube furnace, be warming up to 400-1000 ℃ simultaneously, constant temperature 0.5-5h, finally naturally cool to room temperature, close ammonia, obtain target catalyst;
In described step 1, in every liter of reactant liquor, contain 0.01-1mol cobalt chloride;
In described step 2, with the stereometer of reactant liquor, in one liter of reactant liquor, the addition of acetylene black is 1-100g.
As preferably, in described step 1, in every liter of reactant liquor, contain 0.10mol cobalt chloride.
As preferably, in described step 2, with the stereometer of reactant liquor, in one liter of reactant liquor, the addition of acetylene black is 50g.
As preferably, in described step 2, acetylene black is joined in reactant liquor, mix, stir 30min, then, under the vacuum condition of 50 ℃, dry 2h, obtains presoma.
As preferably, in described step 3, presoma is transferred in tube furnace, first passes into ammonia 20min, the flow of ammonia is 50mL/min, then keep ammonia flow constant, simultaneously to heating up in tube furnace, be warming up to 700 ℃, constant temperature 2h, finally naturally cool to room temperature, close ammonia, obtain target catalyst.
The present invention is directed to foregoing problems, a kind of carbon back non noble metal oxygen reduction catalyst is provided.It is raw material that cobalt chloride, ammonia, acetylene black, absolute ethyl alcohol are take in the present invention, and these raw material sources are extensive, cheap and easy to get, do not adopt the expensive raw materials such as platinum, porphyrin, phthalocyanine, can significantly reduce the cost of catalyst.Meanwhile, method of the present invention is simple to operate, easy to make, and equipment investment is little, can be suitable for the needs of industrialization actual production.
Meanwhile, the present invention has carried out contrast experiment, and experimental result shows, catalyst of the present invention has good oxygen catalytic reduction activity, and has good stability.
Accompanying drawing explanation
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is that the CATALYST Co-Am-C of embodiment 1 preparation is at 0.5M H
2sO
4linear potential scanning curve figure in solution.
Fig. 2 is that the CATALYST Co-Am-C of embodiment 1 preparation is at the saturated 0.5M H of oxygen
2sO
4hydrogen reduction catalytic activity figure in solution.
Fig. 3 is that platinum disk electrode (Ф 2mm, the diameter of platinum disk electrode is 2mm) is at the saturated 0.5M H of oxygen
2sO
4hydrogen reduction catalytic activity figure in solution.
Fig. 4 be the CATALYST Co-Am-C of embodiment 1 preparation and the catalyst n-C of comparative example 1 preparation, catalyst A m-C prepared by comparative example 2 at the saturated 0.5M H of oxygen
2sO
4hydrogen reduction catalytic activity comparison diagram in solution.
The specific embodiment
Disclosed all features in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Disclosed arbitrary feature in this description, unless narration especially all can be replaced by other equivalences or the alternative features with similar object.That is,, unless narration especially, each feature is an example in a series of equivalences or similar characteristics.
In the embodiment of the present invention, prepared oxygen reduction catalyst, its catalytic performance characterizes by electrochemistry linear potential sweep method.
Wherein, electrolyte is the 0.5M H that oxygen is saturated
2sO
4the 0.5M H that solution or nitrogen are saturated
2sO
4solution.
Concrete method of testing is as follows: adopt CHI660D electrochemical workstation (buying from Shanghai Chen Hua instrument company), the electrochemistry three-electrode system of employing standard, the saturated calomel electrode (SCE) of take is reference electrode, and platinized platinum is auxiliary electrode, and glass-carbon electrode is working electrode.During use, catalyst layer on glass-carbon electrode.
The concrete preparation method of working electrode is as follows: after the Nafion solution that is 0.5% by 5mg catalyst fines, 50 μ l mass concentrations, 1ml deionized water are mixed, ultrasonic wave disperses 15min, the slurry drops of then getting after 10 μ l disperse is upper at glass carbon dish (Ф 5mm), naturally dries.
Before electro-chemical test, 0.5M H
2sO
4solution, is tested after saturated 20 minutes with oxygen or nitrogen bubble in 30 ℃ of water-baths, and linear potential sweep speed is 5mV/min.
Take 0.5g CoCl
26H
2o, is dissolved in 20ml absolute ethyl alcohol, obtains reactant liquor.Get again the acetylene black of 1g, acetylene black is joined in reactant liquor, stir 30min, then under the vacuum condition of 50 ℃, dry 2h, obtains presoma.
Then presoma is put into quartz boat, then quartz boat is transferred to the middle part of tube type resistance furnace.First in tube type resistance furnace, pass into ammonia 20min, the flow of ammonia is 50mL/min.Ammonia, now as a kind of protection gas, is conducive to the Bas Discharged in tube type resistance furnace, guarantees the carrying out of subsequent reactions.Then keep the flow of ammonia constant, then heat up to tube type resistance furnace, heating rate is 10 ℃/min, be warming up to after 700 ℃, and constant temperature 2h, thus complete the heat treatment to presoma.After thermostatic process finishes, stop heating in tube furnace, make to naturally cool to room temperature in tube furnace, close ammonia, obtain target catalyst, catalyst prepared by the present embodiment is labeled as Co-Am-C.
Wherein, Fig. 1 is that the CATALYST Co-Am-C of embodiment 1 preparation is at 0.5M H
2sO
4linear potential scanning curve figure in solution.In Fig. 1, be (a) that CATALYST Co-Am-C is at the saturated 0.5M H of oxygen
2sO
4linear potential scanning curve in solution is (b) that CATALYST Co-Am-C is at the saturated 0.5M H of nitrogen
2sO
4linear potential scanning curve in solution.
As can be seen from Figure 1, electric potential scanning is to 0.45V(vs SCE) after start to occur significant cathodic reduction electric current, and at the saturated 0.5M H of oxygen
2sO
4in solution, the cathodic reduction electric current of gained scanning curve is greater than at the saturated 0.5M H of nitrogen
2sO
4the cathodic reduction electric current of the scanning curve in solution, also shows that CATALYST Co-Am-C prepared by embodiment has catalytic activity to oxygen reduction reaction.
Fig. 2 is that the CATALYST Co-Am-C of embodiment 1 preparation is at the saturated 0.5M H of oxygen
2sO
4hydrogen reduction catalytic activity figure in solution, Fig. 3 is that platinum disk electrode (Ф 2mm, the diameter of platinum disk electrode is 2mm) is at the saturated 0.5M H of oxygen
2sO
4hydrogen reduction catalytic activity figure in solution.By comparison diagram 2 and Fig. 3, can find out, the initial hydrogen reduction current potential of the CATALYST Co-Am-C of embodiment 1 preparation is 0.45V(vs SCE) with the initial hydrogen reduction current potential of platinum disk electrode be 0.53V(vs SCE) very approaching, this also shows, the CATALYST Co-Am-C of embodiment 1 preparation has good hydrogen reduction catalytic activity.
Comparative example 1
1g acetylene black is put into after quartz boat, then quartz boat is put into the middle part of tube type resistance furnace.Then in tube type resistance furnace, pass into N
220min, N
2flow be 50mL/min.Then keep N
2flow 50mL/min constant, then heat up to tube type resistance furnace, heating rate is 10 ℃/min, is warming up to after 700 ℃ constant temperature 2h.Then be naturally cooled to room temperature, be cooled to after room temperature, close nitrogen, obtain product.By the product labelling of comparative example 1 preparation, be N-C.
Comparative example 2
1g acetylene black is put into after quartz boat, then quartz boat is put into the middle part of tube type resistance furnace.Then in tube type resistance furnace, pass into NH
320min, NH
3flow be 50mL/min.Then keep NH
3flow 50mL/min constant, then heat up to tube type resistance furnace, heating rate is 10 ℃/min, is warming up to after 700 ℃ constant temperature 2h.Then be naturally cooled to room temperature, be cooled to after room temperature, close NH
3, obtain product.By the product labelling of comparative example 1 preparation, be Am-C.
Fig. 4 be the CATALYST Co-Am-C of embodiment 1 preparation and the catalyst n-C of comparative example 1 preparation, catalyst A m-C prepared by comparative example 2 at the saturated 0.5M H of oxygen
2sO
4hydrogen reduction catalytic activity comparison diagram in solution.
As can be seen from Figure 4, the hydrogen reduction catalytic activity of the CATALYST Co-Am-C of embodiment 1 preparation is significantly improved compared with carbon black.In embodiment 1, cooperatively interacting of cobalt chloride, acetylene black and ammonia is the necessary condition that catalyst heat treatment obtains excellent activity, is also the crystallization of inventor's creative work.
Cobalt chloride is dissolved in absolute ethyl alcohol, is prepared into reactant liquor, in every liter of reactant liquor, contain 0.01mol cobalt chloride.Get acetylene black again, acetylene black is joined in reactant liquor, the addition of acetylene black is with the stereometer of reactant liquor, and one liter of reactant liquor need to add acetylene black 3g, mixes, and stirs 20min, then under the vacuum condition of 80 ℃, dry 1.5h, obtains presoma.
Again presoma is put into quartz boat, quartz boat is transferred to the middle part of tube type resistance furnace.Then in tube type resistance furnace, pass into ammonia 20min, the flow of ammonia is 50mL/min, then keeps the flow of ammonia constant, to tube type resistance furnace, heat up, heating rate is 5 ℃/min, is warming up to after 500 ℃ again, constant temperature 1h, thus the heat treatment to presoma completed.After thermostatic process finishes, stop heating in tube furnace, make to naturally cool to room temperature in tube furnace, close ammonia, obtain product.
Catalyst prepared by the present embodiment detects, and check result shows: it has catalytic activity to oxygen reduction reaction.
Cobalt chloride is dissolved in absolute ethyl alcohol, is prepared into reactant liquor, in every liter of reactant liquor, contain 0.15mol cobalt chloride.Get acetylene black again, acetylene black is joined in reactant liquor, the addition of acetylene black is with the stereometer of reactant liquor, and one liter of reactant liquor need to add acetylene black 25g, mixes, and stirs 40min, then under the vacuum condition of 60 ℃, dry 5h, obtains presoma.
Again presoma is put into quartz boat, quartz boat is transferred to the middle part of tube type resistance furnace.Then in tube type resistance furnace, pass into ammonia 15min, the flow of ammonia is 150mL/min, then keeps the flow of ammonia constant, to tube type resistance furnace, heat up, heating rate is 10 ℃/min, is warming up to after 850 ℃ again, constant temperature 2.5h, thus the heat treatment to presoma completed.After thermostatic process finishes, stop heating in tube furnace, make to naturally cool to room temperature in tube furnace, close ammonia, obtain product.
Catalyst prepared by the present embodiment detects, and check result shows: it has catalytic activity to oxygen reduction reaction.
Cobalt chloride is dissolved in absolute ethyl alcohol, is prepared into reactant liquor, in every liter of reactant liquor, contain 0.5mol cobalt chloride.Get acetylene black again, acetylene black is joined in reactant liquor, the addition of acetylene black is with the stereometer of reactant liquor, and one liter of reactant liquor need to add acetylene black 60g, mixes, and stirs 45min, then under the vacuum condition of 65 ℃, dry 8h, obtains presoma.
Again presoma is put into quartz boat, quartz boat is transferred to the middle part of tube type resistance furnace.Then in tube type resistance furnace, pass into ammonia 30min, the flow of ammonia is 100mL/min, then keeps the flow of ammonia constant, to tube type resistance furnace, heat up, heating rate is 15 ℃/min, is warming up to after 900 ℃ again, constant temperature 3h, thus the heat treatment to presoma completed.After thermostatic process finishes, stop heating in tube furnace, make to naturally cool to room temperature in tube furnace, close ammonia, obtain product.
Catalyst prepared by the present embodiment detects, and check result shows: it has catalytic activity to oxygen reduction reaction.
Cobalt chloride is dissolved in absolute ethyl alcohol, is prepared into reactant liquor, in every liter of reactant liquor, contain 0.8mol cobalt chloride.Get acetylene black again, acetylene black is joined in reactant liquor, the addition of acetylene black is with the stereometer of reactant liquor, and one liter of reactant liquor need to add acetylene black 75g, mixes, and stirs 50min, then under the vacuum condition of 55 ℃, dry 3h, obtains presoma.
Again presoma is put into quartz boat, quartz boat is transferred to the middle part of tube type resistance furnace.Then in tube type resistance furnace, pass into ammonia 25min, the flow of ammonia is 80mL/min, then keeps the flow of ammonia constant, to tube type resistance furnace, heat up, heating rate is 10 ℃/min, is warming up to after 750 ℃ again, constant temperature 1.5h, thus the heat treatment to presoma completed.After thermostatic process finishes, stop heating in tube furnace, make to naturally cool to room temperature in tube furnace, close ammonia, obtain product.
Catalyst prepared by the present embodiment detects, and check result shows: it has catalytic activity to oxygen reduction reaction.
The present invention is not limited to the aforesaid specific embodiment.The present invention expands to any new feature or any new combination disclosing in this manual, and the arbitrary new method disclosing or step or any new combination of process.
Claims (5)
1. a carbon back non noble metal oxygen reduction catalyst, is characterized in that, adopts the method comprising the steps to be prepared from:
The first step: cobalt chloride is dissolved in absolute ethyl alcohol, is prepared into reactant liquor;
Second step: acetylene black is joined in reactant liquor, mix, stir 20-60min, then, under the vacuum condition of 30-80 ℃, dry 1-10h, obtains presoma;
The 3rd step: presoma is transferred in tube furnace, first pass into ammonia 10-30min, the flow of ammonia is 20-500mL/min, then keep ammonia flow constant, to heating up in tube furnace, be warming up to 400-1000 ℃ simultaneously, constant temperature 0.5-5h, finally naturally cool to room temperature, close ammonia, obtain target catalyst;
In described step 1, in every liter of reactant liquor, contain 0.01-1mol cobalt chloride;
In described step 2, with the stereometer of reactant liquor, in one liter of reactant liquor, the addition of acetylene black is 1-100g.
2. carbon back non noble metal oxygen reduction catalyst according to claim 1, is characterized in that, in described step 1, contains 0.10mol cobalt chloride in every liter of reactant liquor.
3. carbon back non noble metal oxygen reduction catalyst according to claim 1, is characterized in that, in described step 2, with the stereometer of reactant liquor, in one liter of reactant liquor, the addition of acetylene black is 50g.
4. carbon back non noble metal oxygen reduction catalyst according to claim 1, is characterized in that, in described step 2, acetylene black is joined in reactant liquor, mixes, and stirs 30min, and then, under the vacuum condition of 50 ℃, dry 2h, obtains presoma.
5. according to carbon back non noble metal oxygen reduction catalyst described in claim 1-4 any one, it is characterized in that, in described step 3, presoma is transferred in tube furnace, first pass into ammonia 20min, the flow of ammonia is 50mL/min, then keeps ammonia flow constant, simultaneously to heating up in tube furnace, be warming up to 700 ℃, constant temperature 2h, finally naturally cools to room temperature, close ammonia, obtain target catalyst.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105375042A (en) * | 2015-12-01 | 2016-03-02 | 沈阳农业大学 | Biomass carbon catalyst and preparation method and application thereof |
| CN111224114A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation and application of carbon-supported bimetallic nitride electrocatalyst |
| CN111490259A (en) * | 2019-01-25 | 2020-08-04 | 苏州沃泰丰能电池科技有限公司 | Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof |
| CN113134354A (en) * | 2021-03-09 | 2021-07-20 | 四川轻化工大学 | Preparation method of high-efficiency oxygen reduction reaction catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105375042A (en) * | 2015-12-01 | 2016-03-02 | 沈阳农业大学 | Biomass carbon catalyst and preparation method and application thereof |
| CN111224114A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation and application of carbon-supported bimetallic nitride electrocatalyst |
| CN111490259A (en) * | 2019-01-25 | 2020-08-04 | 苏州沃泰丰能电池科技有限公司 | Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof |
| CN111490259B (en) * | 2019-01-25 | 2022-05-31 | 苏州沃泰丰能电池科技有限公司 | Nitrogen-doped and defect-containing porous carbon pore channel loaded cobalt cluster material for zinc-air battery and preparation method thereof |
| CN113134354A (en) * | 2021-03-09 | 2021-07-20 | 四川轻化工大学 | Preparation method of high-efficiency oxygen reduction reaction catalyst |
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