CN106099124B - A kind of preparation method of coal base hydrogen reduction carbon catalysis material - Google Patents
A kind of preparation method of coal base hydrogen reduction carbon catalysis material Download PDFInfo
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- CN106099124B CN106099124B CN201610574411.0A CN201610574411A CN106099124B CN 106099124 B CN106099124 B CN 106099124B CN 201610574411 A CN201610574411 A CN 201610574411A CN 106099124 B CN106099124 B CN 106099124B
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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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H—ELECTRICITY
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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 relates to a kind of preparation methods of coal base hydrogen reduction carbon catalysis material, are crushed to more than 1000 mesh to coal material；Sour processing is carried out to coal material, the acid processing is to be handled using hydrofluoric acid, nitric acid or phosphoric acid；Processing procedure uses acid solution body and/or acid vapor：A acid liquid handlings stand or stir under the conditions of room temperature or temperature are 60~90 DEG C, carried out under the conditions of 2~12 hours；B is handled using acid vapor, in 120~200 DEG C of temperature, is carried out under the conditions of 12~72 hours.Advantage is：Synthesis technology is simple, and manufacturing cost is low, abundant raw material and cheap.It can be used for the high added value hydrogen reduction carbon catalysis material of fuel cell.There is synergistic effect in the presence of the Heteroatom doping coal base hydrogen reduction carbon catalysis material for prepare while transition metal, nitrogen and carbon, can realize good electrocatalytic oxidation reduction reaction.
Description
Technical field
The invention belongs to the deep processings of traditional coal resources and high value added utilization field more particularly to one kind can be applied to
The preparation method of the coal base hydrogen reduction carbon catalysis material of fuel battery cathode material.
Background technology
The rapid growth of world economy makes energy shortage problem also increasingly serious.Therefore, develop all kinds of renewable greens
New energy, such as fuel cell etc. becomes the important focus of this century people research.Past fuel cell related field
Main developing direction of making great efforts is to improve the performance of fuel-cell catalyst and reduce fuel-cell catalyst cost, this is because passing
System fuel cell reaction needs to use precious metal platinum and its alloy.However due to its resource limitation on earth, exploitation
Non-precious metal catalyst, such as the carbon modified composite material haveing excellent performance can industrialize greatly as substitute as fuel cell
The inexorable trend of production and application.At the same time, the deep processing of traditional coal resources and high value added utilization are coalifications in recent years
The research hotspot in work field.
Therefore, using the abundant coal resources in China as raw material, deep processing is carried out to it, is further prepared high additional
The oxygen reduction electro-catalyst that can be used for green novel energy source fuel cell of value not only has the business application of fuel cell important
Meaning more has significant contribution to the sustainable development of natural environment for the survival of mankind and energy resources.
Invention content
In order to overcome the deficiencies of the prior art, the object of the present invention is to provide a kind of preparations of coal base hydrogen reduction carbon catalysis material
Method, technical process is simple, at low cost, avoids traditional coal burning and obtains environmental pollution caused by energy and resource wave
Take.
To achieve the above object, the invention is realized by the following technical scheme：
A kind of preparation method of coal base hydrogen reduction carbon catalysis material, includes the following steps：
1) coal material is crushed to more than 1000 mesh；
2) sour processing is carried out to coal material, the acid processing is to be handled using hydrofluoric acid, nitric acid or phosphoric acid；Place
Reason process uses acid solution body and/or acid vapor：A acid liquid handlings stand or stir under the conditions of room temperature or temperature are 60~90 DEG C
It mixes, is carried out under the conditions of 2~12 hours；B is handled using acid vapor, in 120~200 DEG C of temperature, under the conditions of 12~72 hours into
Row；
3) under the mixed atmosphere of ammonia and inert gas at 600~1000 DEG C high-temperature process 1~3 hour；It crosses herein
Cheng Zhong, heating rate are controlled in 2~10 DEG C/min；Air velocity is 20~200sccm；
4) mixed gas protected in inert gas or ammonia and inert gas through step 3) treated coal material
Lower Temperature fall, the product taken out in reactor is coal base hydrogen reduction carbon catalysis material；In coal base hydrogen reduction carbon catalysis material
The mass content of nitrogen is 1.6% to 9.3%, and the existing way of nitrogen is pyridine nitrogen, pyrroles's nitrogen and graphitization nitrogen；
5) after step 2), further by the processed coal material of acid and iron, cobalt, nickel, manganese transition metal salt
After one or two kinds of mixtures are blended, then the processing of step 3), step 4) is carried out successively, finally obtained transition metal complex coal base
Hydrogen reduction carbon catalysis material.
Coal material described in step 1) is anthracite, bituminous coal, lignite.
The mass ratio of coal material and acid is 1 in step 2):5~1:1；The mass ratio of coal material and acid vapor is 1:20
~1:1.
The volume ratio of ammonia and inert gas is 1 in step 3):10~1:1.
The volume ratio of ammonia and inert gas is 1 in the step 4) ammonia and inert gas gaseous mixture:10~1:1.
The mass ratio of step 5) metallic element and acid treated coal material is 1:500~1:10.
The inert gas is nitrogen, argon gas or helium.
Compared with prior art, the beneficial effects of the invention are as follows：
The synthesis technology of the present invention is simple, and manufacturing cost is low, abundant raw material and cheap.The low value coal abundant to china natural resources
Charcoal carries out deep processing and improves its added value, is prepared for can be used for the high added value hydrogen reduction carbon catalysis material of fuel cell.Transition
In the presence of the Heteroatom doping coal base hydrogen reduction carbon catalysis material for prepare there is collaboration to imitate while metal, nitrogen and carbon
It answers, can realize good electrocatalytic oxidation reduction reaction.
Description of the drawings
Fig. 1 is the scanning electron microscopic picture of coal base hydrogen reduction carbon catalysis material.
Fig. 2 is original coal material by the pretreated coal of concentrated nitric acid and by concentrated nitric acid low-kappa number and ammonia height
Warm handles the elemental analysis figure of later coal base hydrogen reduction carbon catalysis material.
Fig. 3 is original coal material, by liquid hydrofluoric acid and concentrated nitric acid steam pre-treatment and using ammonia high temperature
It is heat-treated the Raman comparison collection of illustrative plates of later coal base hydrogen reduction carbon catalysis material.
Fig. 4 is original coal material, coal base hydrogen reduction carbon catalysis material and later with transition metal iron elements compounding
The XPS N1s of coal base hydrogen reduction carbon catalysis material compare collection of illustrative plates.
Fig. 5 is original coal material, coal base hydrogen reduction carbon catalysis material and later with transition metal iron elements compounding
The XPS Fe2p of coal base hydrogen reduction carbon catalysis material compare collection of illustrative plates.
Fig. 6 is to detect the original coal material of gained, coal base oxygen also using linear scanning method and rotating ring disk electrode (r.r.d.e) combination
The hydrogen reduction of former carbon catalysis material and the coal base hydrogen reduction carbon catalysis material later with transition metal iron elements compounding linearly lies prostrate
Pacify curve comparison figure.
Specific implementation mode
The present invention is described in detail with reference to the accompanying drawings of the specification, it should be noted that the implementation of the present invention is unlimited
In the following embodiments and the accompanying drawings.
Embodiment 1
Using Xinjiang lignite as raw material, it is ground first with agate mortar and is crushed to 1000 mesh or more；So
Sour processing is carried out to it using concentrated nitric acid steam afterwards, the ratio control of coal sample and concentrated nitric acid liquid is 1:20, acid is processed
Cheng Chixu 24 hours, acid liquor temperature are controlled at 150 DEG C；Sample is then put into horizontal-type high temperature reacting furnace, is passed through ammonia and nitrogen
(air velocity 100sccm, ammonia and nitrogen volume ratio are 1 to mixed gas:4) it, is heated to the heating rate of 5 DEG C/min
900 DEG C, and for 3 hours, allow later sample under conditions of nitrogen protection cooled to room temperature to get to can be used for firing
The hydrogen reduction carbon catalysis material for expecting battery, is shown in Fig. 1.Elemental analysis is the result shows that preparing after ammonia high-temperature heat treatment
Coal base hydrogen reduction carbon catalysis material nitrogen content obviously rises, and hydrogeneous and oxygen content is substantially reduced, and sees Fig. 2.
Embodiment 2
Using Inner Mongol lignite as raw material, it is ground first with agate mortar and is crushed to 1000 mesh or more；
Then sour processing is carried out to sample using dense hydrofluoric acid, coal sample with mass ratio 1:5 are mixed with hydrofluoric acid, at 60 DEG C
Under the conditions of keep 6 hours, later with a large amount of clear water cleaning samples to pH value be 6.5~7.5 between；Then recycle concentrated nitric acid
Steam carries out it quadratic acid processing, and the ratio control of coal sample and concentrated nitric acid liquid is 1:10, sour processing procedure continues 24
Hour, acid liquor temperature is controlled at 150 DEG C；Sample is then put into horizontal-type high temperature reacting furnace, is passed through ammonia and nitrogen mixed gas
(air velocity 100sccm, volume ratio 1:10) 900 DEG C, are heated to the heating rate of 5 DEG C/min, and is continued 3 small
When, allow later sample under conditions of nitrogen protection cooled to room temperature to get to the hydrogen reduction carbon that can be used for fuel cell
Catalysis material.Raman is prepared the result shows that passing through acid solution body and steam pre-treatment after being heat-treated later using high temperature ammonia
Hydrogen reduction carbon catalysis material compared to original coal have higher surface and edge shortcoming, see Fig. 3.
Embodiment 3
Using Heilungkiang bituminous coal as raw material, it is ground first with agate mortar and is crushed to 1000 mesh or more；
Then sour processing is carried out to sample using dense hydrofluoric acid, coal sample with mass ratio 1:5 are mixed with hydrofluoric acid, at 60 DEG C
Under the conditions of keep 2 hours, later with a large amount of clear water cleaning samples to pH value be 6.5~7.5 between；Then recycle concentrated nitric acid
Steam carries out it quadratic acid processing, and sour processing procedure continues 24 hours, and acid liquor temperature is controlled at 200 DEG C；Then sample with
Acetic acid iron salt solutions mix (weight of iron accounts for the 1% of coal sample in ferric acetate) and dry 2 small in the drying box for being set as 80 DEG C
When；Take out mixing sample and be simultaneously put into horizontal-type high temperature reacting furnace, be passed through ammonia and nitrogen mixed gas (air velocity 150sccm,
Volume ratio is 1:3) 800 DEG C, are heated to the heating rate of 2 DEG C/min, and for 2 hours, sample is allowed to be protected in nitrogen later
Cooled to room temperature is to get to the compound coal-based carbon catalysis material of transition metal iron under conditions of shield.See Fig. 4, XPS N 1s
The result shows that the sample nitrogen content after Ammonia gas disposal obviously increases, and with trace iron while introduces, and nitrogen content is slightly
It reduces.See Fig. 5, XPS Fe 2p spectrograms are the result shows that original coal sample contains micro ferro element, and the pretreatment of acid is stripped of portion
Point iron, but mixed again with transition metal molysite, hence it is evident that increase content of the iron in the catalysis material of preparation.
Embodiment 4
Using Guizhou anthracite as raw material, it is ground first with agate mortar and is crushed to 1000 mesh or more；
Then sour processing is carried out to sample using dense hydrofluoric acid, coal sample with mass ratio 1:2 are mixed with hydrofluoric acid, at 60 DEG C
Under the conditions of keep 12 hours, later with a large amount of clear water cleaning samples to pH value be 6.5~7.5 between；Then recycle dense nitre
Acid vapor carries out it quadratic acid processing, and sour processing procedure continues 24 hours, and acid liquor temperature is controlled at 150 DEG C；Then sample
It is mixed with ferrum sulfuricum oxydatum solutum (weight of iron accounts for the 2% of coal sample in ferric sulfate) and dry 2 small in the drying box for being set as 80 DEG C
When；Take out mixing sample and be simultaneously put into horizontal-type high temperature reacting furnace, be passed through ammonia and nitrogen mixed gas (air velocity 150sccm,
Volume ratio is 2:3) 800 DEG C, are heated to the heating rate of 10 DEG C/min, and for 2 hours, sample is allowed to be protected in nitrogen later
Cooled to room temperature is to get to the compound coal-based carbon catalysis material of transition metal iron under conditions of shield.Using three-electrode system
Electrochemical workstation, utilize rotating disk electrode (r.d.e) and linear scanning method joint technology, measure coal base hydrogen reduction carbon catalysis material
Hydrogen reduction performance under alkaline condition, the results are shown in Figure 6.Under the sweep speed of 5mV/s, coal base hydrogen reduction carbon is catalyzed material
Material has good oxygen reduction catalytic activity and selectivity under alkaline condition, and hydrogen reduction electron transfer number is about 4.
Embodiment 5
Coal base hydrogen reduction carbon catalysis material is made by coal material of Liaoning bituminous coal, making step is：
1) bituminous coal is ground with agate mortar and is crushed to 1000 mesh or more；
2) hydrofluoric acid treatment is carried out to bituminous coal, coal is 1 with sour mass ratio:1, it is being stored at room temperature, under the conditions of 12 hours
It carries out；Later with a large amount of clear water cleaning samples to pH value be 6.5~7.5 between；
3) in ammonia and inert gas (volume ratio 1:1) it handles in 600 DEG C under mixed atmosphere 1 hour, in the process, rises
Warm speed control is in 10 DEG C/min；Air velocity is 20sccm；Wherein, inert gas selects argon gas；
4) through step 3) treated bituminous coal, Temperature fall under protection of argon gas, the product taken out in reactor is coal
Base N doping hydrogen reduction carbon catalysis material；The mass content of nitrogen is 1.6% in coal base N doping hydrogen reduction carbon catalysis material, nitrogen
Existing way is pyridine nitrogen, pyrroles's nitrogen and graphitization nitrogen；
5) after step 2), step then is further carried out by the processed bituminous coal of acid successively with after cobalt nitrate salt blend
3) transition metals cobalt complex coal base hydrogen reduction carbon catalysis material is finally made in, the processing of step 4).
Embodiment 6
Coal base hydrogen reduction carbon catalysis material is made by coal material of Yunnan lignite, making step is：
1) coal material is ground with agate mortar is crushed to 1000 mesh or more；
2) hydrofluoric acid treatment is carried out to coal material, coal is 1 with sour mass ratio:1, it is being stored at room temperature, 2 hours conditions
Lower progress；Later with a large amount of clear water cleaning samples to pH value be 6.5~7.5 between；
3) in ammonia and inert gas (volume ratio 1:5) under mixed atmosphere in 1000 DEG C handle 3 hours, in the process,
Heating rate is controlled in 2 DEG C/min；Air velocity is 200sccm；Wherein, inert gas selects nitrogen；
4) through step 3) treated coal material, Temperature fall under nitrogen protection, the product taken out in reactor is i.e.
For coal base N doping hydrogen reduction carbon catalysis material；The mass content of nitrogen is 9.3% in coal base N doping hydrogen reduction carbon catalysis material,
The existing way of nitrogen is pyridine nitrogen, pyrroles's nitrogen and graphitization nitrogen.
Through above-described embodiment treated coal material, coal base N doping hydrogen reduction carbon catalysis material is obtained, in the material
Nitrogen exists in a manner of pyridine nitrogen, pyrroles's nitrogen and graphitization nitrogen, and mass content of the nitrogen in the catalysis material is 1.6%-
9.3%.Embodiment 3 and embodiment 4, embodiment 5 are blended through one or both of iron, cobalt, nickel, manganese transition metal salt mixture
Afterwards, transition metal complex coal base hydrogen reduction carbon catalysis material is finally made.Transition metal salt be nitrate, sulfate, chlorate,
Any inorganic and organic salt containing above-mentioned transition metal element of carbonate, acetate.
Claims (7)
1. a kind of preparation method of coal base hydrogen reduction carbon catalysis material, which is characterized in that include the following steps：
1) coal material is crushed to more than 1000 mesh；
2) sour processing is carried out to coal material, the acid processing is to be handled using hydrofluoric acid, nitric acid or phosphoric acid；It is processed
Cheng Caiyong acid solutions body and/or acid vapor：A acid liquid handlings stand or stir, 2 under the conditions of room temperature or temperature are 60~90 DEG C
It is carried out under the conditions of~12 hours；B is handled using acid vapor, in 120~200 DEG C of temperature, is carried out under the conditions of 12~72 hours；
3) under the mixed atmosphere of ammonia and inert gas at 600~1000 DEG C high-temperature process 1~3 hour；In the process,
Heating rate is controlled in 2~10 DEG C/min；Air velocity is 20~200sccm；
4) through step 3) treated coal material, inert gas or ammonia and inert gas it is mixed gas protected it is lower from
So cool down, the product taken out in reactor is coal base hydrogen reduction carbon catalysis material；Nitrogen in coal base hydrogen reduction carbon catalysis material
Mass content is 1.6% to 9.3%, and the existing way of nitrogen is pyridine nitrogen, pyrroles's nitrogen and graphitization nitrogen；
5) or after step 2), further pass through the processed coal material of acid and one in iron, cobalt, nickel, manganese transition metal salt
After kind or two kinds of mixtures are blended, then the processing of step 3), step 4) is carried out successively, finally obtained transition metal complex coal base oxygen
Restore carbon catalysis material.
2. a kind of preparation method of coal base hydrogen reduction carbon catalysis material according to claim 1, which is characterized in that step 1)
The coal material is anthracite, bituminous coal or lignite.
3. a kind of preparation method of coal base hydrogen reduction carbon catalysis material according to claim 1, which is characterized in that step 2)
The mass ratio of middle coal material and acid is 1:5~1:1；The mass ratio of coal material and acid vapor is 1:20~1:1.
4. a kind of preparation method of coal base hydrogen reduction carbon catalysis material according to claim 1, which is characterized in that step 3)
The volume ratio of middle ammonia and inert gas is 1:10~1:1.
5. a kind of preparation method of coal base hydrogen reduction carbon catalysis material according to claim 1, which is characterized in that step 4)
The volume ratio of ammonia and inert gas is 1 in the ammonia and inert gas gaseous mixture:10~1:1.
6. a kind of preparation method of coal base hydrogen reduction carbon catalysis material according to claim 1, which is characterized in that step 5)
The mass ratio of metallic element and acid treated coal material is 1:500~1:10.
7. a kind of preparation method of coal base hydrogen reduction carbon catalysis material according to claim 1, which is characterized in that described
Inert gas is nitrogen, argon gas or helium.
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| WO2018099173A1 (en) * | 2016-12-02 | 2018-06-07 | 建添企业有限公司 | Method for preparing nitrogen-doped porous carbon material by using coal as raw material |
| CN110061199B (en) * | 2018-01-19 | 2023-08-01 | 湖南晋烨高科股份有限公司 | Metal-carbon composite anode material and preparation method and application thereof |
| CN111036264B (en) * | 2019-12-11 | 2022-06-28 | 太原理工大学 | Preparation method of coal-based carbon nanotube catalyst for efficiently catalyzing and oxidizing toluene |
| CN110943232B (en) * | 2019-12-26 | 2021-01-05 | 辽宁科技大学 | Preparation method of metal air battery electrocatalyst based on coal self-growing carbon nano tube |
| CN112499613B (en) * | 2020-12-30 | 2022-04-26 | 中国矿业大学 | Preparation method of nitrogen and phosphorus doped porous carbon for wide pH range oxygen reduction electrocatalysis |
| CN112892549B (en) * | 2021-01-25 | 2022-03-01 | 天津大学 | Catalyst for treating sewage by electrocatalytic oxidation and preparation method thereof |
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