CN107369840A - A kind of atom level disperses the preparation method of non-noble metal fuel cell cathod catalyst - Google Patents
A kind of atom level disperses the preparation method of non-noble metal fuel cell cathod catalyst 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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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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
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Abstract
The invention belongs to electrochemical catalysis field, and disclose the preparation method that a kind of atom level disperses non-noble metal fuel cell cathod catalyst.This method comprises the following steps：(a) it is alginate solution to dissolve by heating alginate, keeps heating-up temperature and metal salt is added in alginate solution, generate alginate chelate solution；(b) organic nitrogen compound is added in alginate chelate solution, the two reacts and is evaporated to obtain powdered compounds by reacted product；(c) powdered compounds are carried out with first time heat treatment, pickling successively and is heat-treated for second, required catalyst is thus made.By the present invention, the catalyst for possessing very high activity in acid medium is prepared, realizes itself by the dispersed fixation of avtive spot, easily regulation and control, suitable for large-scale production and use.
Description
Technical field
The invention belongs to electrochemical catalysis field, disperses non-noble metal fuel cell more particularly, to a kind of atom level
The preparation method of cathod catalyst.
Background technology
Oxygen reduction reaction (acid solution O2+4H++4e-→H2O, alkaline solution O2+2H2O+4e-→4OH-) it is development fuel
Battery obtains the important reaction of clean energy resource research, and is also at present the biggest obstacle for hindering commercializing fuel cells, compared to
The oxygen evolution reaction of anode, the dynamics of hydrogen reduction are slow.Only have a series of noble metals and precious metal alloys could effectively at present
Catalytic cathode oxygen reduction reaction, and noble metal price be present high, resource-constrained, not good etc. enough outstanding problem of stability, resistance
The commercialized development of Proton Exchange Membrane Fuel Cells is hindered.For this level, for the moon of Proton Exchange Membrane Fuel Cells
Pole oxygen reduction reaction, development low cost, aboundresources, the good non-precious metal catalyst of stability could be solved fundamentally at present
The commercialized problem of Proton Exchange Membrane Fuel Cells.
Recent studies indicate that the C catalyst based on transition metal (iron, cobalt, nickel) doping nitrogen is anti-in catalytic oxidation-reduction
Preferable activity should be shown, therefore many researchers have carried out many work, also achieve preferable development, such as activity
Improve, control of pattern etc..Many study mechanisms show that the reason for activity is high is that the carbon of N doping has higher ratio table
Area, electrical conductivity, and high-throughout mass transport.However, it is dispersed and in catalytic process to prepare avtive spot
In avoid the catalyst report itself reunited less, and there is high activity and stability in acid medium be even more it is few again
It is few.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of atom level to disperse base metal combustion
Expect the preparation method of cell cathode catalyst, occur by using the alginate similar to dispersant and transition-metal cation
" self-locking " reaction forms chelate, so as to being dispersed in iron atom level in carbon matrix, is then re-introduced into nitrogen source, can obtain
More avtive spots are obtained, thus solve the dispersed technical problem of avtive spot.
To achieve the above object, it is proposed, according to the invention, provide a kind of scattered non-noble metal fuel cell negative electrode of atom level and urge
The preparation method of agent, it is characterised in that the preparation method comprises the following steps：
(a) it is alginate solution to dissolve by heating alginate, keeps the heating-up temperature and molten in the alginate
Metal salt is added in liquid, thus generates alginate chelate solution；
(b) organic nitrogen compound is added in the alginate chelate solution as made from step (a), the two reacts and will be anti-
Product after answering is evaporated to obtain powdered compounds；
(c) powdered compounds are carried out with first time heat treatment, pickling successively and is heat-treated for second, is made required
Catalyst, thus complete needed for catalyst preparation.
It is further preferred that in step (a), the mol ratio of the alginate and metal salt is 1/4~16:1, its
In, the mole of alginate is calculated according to a molecular cell.
It is further preferred that in step (a), the temperature range of the heating is 30 DEG C~100 DEG C.
It is further preferred that in step (a), the metal salt uses FeCl3、Fe(NO3)3Or Fe (CH3COO)2In
A kind of or combination.
It is further preferred that in step (b), the organic nitrogen compound of addition is 1 with the mol ratio of the metal salt
~32:1.
It is further preferred that in step (b), the organic nitrogen compound is ethylenediamine, melamine, cyanamide or dicyandiamide
In one kind or combination.
It is further preferred that in step (c), the first time and second of heat treatment temperature are 300 DEG C~1200
DEG C, soaking time is 0.5h~12h.
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect：
1st, the present invention, can when running into metal cation by using the alginate similar to dispersant, alginate
Reacted with occurring to be similar to " self-locking ", its principle is that four alginate molecules surround metal cation to form class diamond sky
Chamber, so as to will one by one metal cation it is monoatomic it is scattered in the solution and form metal salt chelate, reach fine dispersion
The purpose of avtive spot, and the avtive spot of single atomic dispersion will not produce polymerization during reaction, solve at present
The problem of the preparing low yield of single atomic dispersion catalyst for first preparing cavity and introducing metallic atom preparation again used, method
It is simple and practical, and then catalyst is also possessed higher stability while with outstanding ORR activity；
2nd, the present invention has the catalyst of high activity by preparing in acid medium, and prior art is simply applied to alkalescence
In medium, and the exchange membrane of alkaline medium is not as good as the exchange membrane technology mature of acid medium, therefore prepares in acid medium
In possess very high activity catalyst it is significant, why the present invention can show outstanding ORR activity in acidity, benefit
There is high specific surface area in catalyst, and the scattered of atom level forms Fe-NXCoordination structure is main avtive spot, atom
The dispersed of level provides more exposed points, and so as to possess excellent catalytic activity, good Activity and stabill also obtains
The avtive spot disperseed beneficial to atom level is surrounded by carbon matrix, is dissolved and is rolled into a ball by acid medium during the course of the reaction so as to avoid
It is poly-；
3rd, the present invention is handled powdered compounds by using first time and second of heat treatment, for the first time at heat
Reason is the mixture of solution stirring being carbonized in high temperature, also completes the introducing of nitrogen source, and heat treatment is important for the second time
Part is that unstable phase can will be removed after pickling forms more bigger serface, more preferable degree of graphitization afterwards；
4th, for the present invention first by being dissolved by heating to alginate, otherwise alginate is not soluble in water, can cause shape
Into chelate be difficult to stir, for catalyst it is follow-up preparation have a great influence, can be difficult to the avtive spot in catalyst first
It is dispersed, so as to reduce activity；Meanwhile temperature also can play pass to the combination degree of alginate and transition-metal cation
Key acts on, and ion can be caused to reunite when subsequent treatment if combination degree is weak；
5th, the lower cost for material selected in the present invention, aboundresources, secondary pollution, the work of preparation will not be caused to environment
Skill program is simple, can be with equal proportion quantization operation, and the condition of experiment is without rigors, and the catalyst prepared is in acid condition
Possess very high oxygen reduction activity, possess good stability in addition, the catalyst of our preparations of the present invention is by 5000 circles
After accelerated stability test, half wave potential and carrying current do not change substantially, compared with existing non-precious metal catalyst
It is very rare, it is adapted to following commercialized large-scale production.
Brief description of the drawings
Fig. 1 is the flow chart according to the preparation method constructed by the preferred embodiments of the present invention；
Fig. 2 is according to the AB-Fe-N oxygen reduction catalyst SEM electron microscopes constructed by the preferred embodiments of the present invention；
Fig. 3 is the polarization curves of oxygen reduction figure according to the AB-Fe-N catalyst constructed by the preferred embodiments of the present invention；
Fig. 4 is the polarization curve according to the AB-Fe-N catalyst cyclical stabilities constructed by the preferred embodiments of the present invention
Figure.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below
Conflict can is not formed each other to be mutually combined.
Fig. 1 is according to the flow chart of the preparation method constructed by the preferred embodiments of the present invention, as shown in figure 1, a kind of high
Molecularly Imprinted Polymer alginate (Alginate Blends), also known as alginic acid glue, following alginate are referred to as AB, wherein sea
The molal quantity of alginates is 0.0015~0.099mol, and the molal quantity of alginate is calculated with a molecular cell, passes through magnetic
Power agitator is dissolved in 30 DEG C~100 DEG C of ultra-pure water, forms the solution of homogeneous transparent.Then by 0.006mol gold
Belong to salt (such as FeCl3、Fe(NO3)3、Fe(CH3COO)2, NiCl2Or Co (NO3)3Deng) add homogeneous transparent alginate solution
In, after above-mentioned solution stirs 0.5h~72h, add the nitrogenous presomas of 0.006~0.198mol, (such as ethylenediamine, melamine
Amine, cyanamide, dicyandiamide etc.), all solution add after the completion of 30 DEG C~100 DEG C temperature ranges carry out constant temperature stirring 0.5h~
120h, then constant temperature is evaporated in open container, is ground afterwards, is heat-treated in tube furnace, is passed through protectiveness gas
Body, such as nitrogen, argon gas etc., temperature range are 300 DEG C~1200 DEG C, and the heating-up time is 30min~120min, soaking time 0.5h
~12h, sample after heat treatment take out after in 50 DEG C~100 DEG C of 0.5M H2SO4The pickling 12h that flows back is carried out in round-bottomed flask,
Vacuum drying 0.5h~24h is carried out after taking-up, by the sample after grinding be placed again into tube furnace carry out self-consistentency 300~
1200 DEG C of temperature ranges are heat-treated, that is, obtain the highly reactive form of oxygen reduction catalyst with fine dispersion.
The present invention is described further below in conjunction with specific embodiments.
Case study on implementation 1
Weigh 0.0015mol alginates to be dissolved in 80 DEG C of water, after homogeneous transparent solution is formed, add 0.006mol
FeCl3Molysite, the chelate of flocculence is formed, after stirring 10 hours, add 0.006mol nitrogen presoma ethylenediamine, then stir
Mix 48 hours, open container is evaporated, obtain powdered catalyst, be then placed in tube furnace and carry out heat at 700 DEG C
Processing, nitrogen is passed through as protective gas, 5 DEG C/min of heating rate, 2 hours is incubated, is put into 0.5M sulfuric acid to enter after taking-up
Row pickling carries out 12h at 100 DEG C, and vacuum drying 12h is carried out after taking-up, then places into stove by above-mentioned heat treatment, obtains most
Whole catalyst.
Case study on implementation 2
Weigh 0.099mol alginates to be dissolved in 50 DEG C of water, after homogeneous transparent solution is formed, add 0.006mol
Co (NO3)3Salt, the chelate of flocculence is formed, after stirring 10 hours, add 0.198mol nitrogen presoma cyanamide, be stirred for
48 hours, open container is evaporated, obtains powdered catalyst, be then placed in tube furnace and carry out hot place at 1200 DEG C
Reason, nitrogen is passed through as protective gas, 10 DEG C/min of heating rate, 5 hours is incubated, is put into 0.5M sulfuric acid and carries out after taking-up
Pickling carries out 24h at 100 DEG C, and vacuum drying 10h is carried out after taking-up, then places into stove by above-mentioned heat treatment, obtains final
Catalyst.
Case study on implementation 3
Weigh 0.05025mol alginates to be dissolved in 30 DEG C of water, after homogeneous transparent solution is formed, add
0.006mol Fe (NO3)3Molysite, the chelate of flocculence is formed, after stirring 10 hours, add 0.102mol nitrogen presoma
Dicyandiamide, it is stirred for 48 hours, open container is evaporated, obtain powdered catalyst, be then placed in tube furnace
1200 DEG C are heat-treated, and are passed through nitrogen as protective gas, 5 DEG C/min of heating rate, are incubated 2 hours, are put into after taking-up
Pickling is carried out in 0.5M sulfuric acid and carries out 12h at 100 DEG C, vacuum drying 12h is carried out after taking-up, then places into stove by above-mentioned
Heat treatment, obtains final catalyst.
Case study on implementation 4
Weigh 0.00792mol alginates to be dissolved in 100 DEG C of water, after homogeneous transparent solution is formed, add
0.006mol Fe (NO3)3Molysite, the chelate of flocculence is formed, after stirring 10 hours, add 0.1584mol nitrogen presoma
Melamine, it is stirred for 48 hours, open container is evaporated, obtain powdered catalyst, be then placed in tube furnace
It is heat-treated at 1200 DEG C, is passed through nitrogen as protective gas, 5 DEG C/min of heating rate, is incubated 12 hours, is put into after taking-up
Pickling is carried out in 0.5M sulfuric acid and carries out 12h at 100 DEG C, vacuum drying 12h is carried out after taking-up, then places into stove by above-mentioned
Heat treatment, obtains final catalyst.
Case study on implementation 5
Weigh 0.0495mol alginates to be dissolved in 70 DEG C of water, after homogeneous transparent solution is formed, add 0.006mol
NiCl2Salt, the chelate of flocculence is formed, after stirring 10 hours, add 0.12375mol nitrogen presoma melamine, then
Stirring 72 hours, is evaporated with regard to open container, obtains powdered catalyst, is then placed in tube furnace in 900 DEG C of progress
Heat treatment, nitrogen is passed through as protective gas, 5 DEG C/min of heating rate, 2 hours is incubated, is put into after taking-up in 0.5M sulfuric acid
Carry out pickling and carry out 12h at 100 DEG C, vacuum drying 12h is carried out after taking-up, then place into stove by above-mentioned heat treatment, obtain
Final catalyst.
Case study on implementation 6
Weigh 0.072mol alginates to be dissolved in 65 DEG C of water, after homogeneous transparent solution is formed, add 0.003mol
NiCl2Salt and 0.003mol Fe (NO3)3Salt, the chelate of flocculence is formed, after stirring 10 hours, add 0.012mol's
Nitrogen presoma melamine and 0.024mol dicyandiamides, it is stirred for 0.5 hour, open container is evaporated, obtains powdered
Catalyst, be then placed in tube furnace and be heat-treated at 900 DEG C, be passed through nitrogen as protective gas, 5 DEG C of heating rate/
Min, 2 hours are incubated, progress pickling in 0.5M sulfuric acid is put into after taking-up and carries out 12h at 100 DEG C, is dried in vacuo after taking-up
12h, then place into stove by above-mentioned heat treatment, obtain final catalyst.
Case study on implementation 7
Weigh 0.090mol alginates to be dissolved in 40 DEG C of water, after homogeneous transparent solution is formed, add 0.006mol
NiCl2Salt, forms the chelate of flocculence, after stirring 10 hours, add 0.036mol nitrogen presoma melamine and
0.006mol cyanamides, it is stirred for 0.5 hour, open container is evaporated, obtain powdered catalyst, be then placed in tubular type
It is heat-treated in stove at 900 DEG C, is passed through nitrogen as protective gas, 5 DEG C/min of heating rate, is incubated 2 hours, is put after taking-up
Enter to carry out pickling in 0.5M sulfuric acid to carry out 12h at 100 DEG C, carry out vacuum drying 12h after taking-up, then place into stove by upper
Heat treatment is stated, obtains final catalyst.
Case study on implementation 8
Weigh 0.05025mol alginates to be dissolved in 50 DEG C of water, after homogeneous transparent solution is formed, add
0.001mol Co (NO3)3Salt and 0.005mol Fe (NO3)3, the chelate of flocculence is formed, after stirring 10 hours, is added
0.006mol nitrogen presoma melamine and 0.012mol dicyandiamides, is stirred for 0.5 hour, is evaporated with regard to open container,
Powdered catalyst is obtained, is then placed in tube furnace and is heat-treated at 600 DEG C, nitrogen is passed through as protective gas, rises
Warm 5 DEG C/min of speed, 2 hours are incubated, progress pickling in 0.5M sulfuric acid is put into after taking-up and carries out 12h at 100 DEG C, is taken out laggard
Row vacuum drying 12h, then places into stove by above-mentioned heat treatment, obtains final catalyst.
Case study on implementation 9
Weigh 0.024mol alginates to be dissolved in 90 DEG C of water, after homogeneous transparent solution is formed, add 0.006mol
Fe (CH3COO)2, form the chelate of flocculence, after stirring 10 hours, add 0.048mol nitrogen presoma ethylenediamine and
0.054mol cyanamides, it is stirred for 0.5 hour, open container is evaporated, obtain powdered catalyst, be then placed in tubular type
It is heat-treated in stove at 600 DEG C, is passed through nitrogen as protective gas, 5 DEG C/min of heating rate, is incubated 1 hour, is put after taking-up
Enter to carry out pickling in 0.5M sulfuric acid to carry out 12h at 100 DEG C, carry out vacuum drying 12h after taking-up, then place into stove by upper
Heat treatment is stated, obtains final catalyst.
Fig. 2 is according to the AB-Fe-N oxygen reduction catalyst SEM electron microscopes constructed by the preferred embodiments of the present invention, such as Fig. 2
It is shown, it is that obtained final catalyst is characterized by transmission electron microscope, has obtained the flake graphite structure of accordion,
Also there is multi-layer classification holes mechanism simultaneously, the graphite-structure of thin slice first can increase specific surface area, and foot is provided for avtive spot
Enough carbon matrix, and catalyst form the necessary condition of single atomic dispersion, and the graded porous structure seen in figure is (including micro-
Hole, mesoporous and macropore) key effect is also played for catalytic reaction, micropore more can must provide potential avtive spot, and
Mesoporous to provide more preferable mass transfer for reactant and product with macropore, this is the greater advantage of the present invention.
Single atomic dispersion catalyst prepared by the present invention is compared to current most active site with existing for graininess
Catalyst and the catalyst for not introducing alginate preparation, can more haptoreaction thing, exposed more avtive spots,
More advantages are given play to, Fig. 3 is the hydrogen reduction polarization according to the AB-Fe-N catalyst constructed by the preferred embodiments of the present invention
Curve map, as shown in figure 3, either introducing alginate from half wave potential or carrying current as we can clearly see from the figure
Sample all possess very big advantage, and both is exactly two great reference indexs of fuel cell oxygen reduction activity, so
We can show that the single atomic dispersion catalyst of the present invention has very high advantage.
For the commercial applications of fuel cell, stability test is also an important parameter, therefore we
Influence of the catalyst of the present invention for stability test is tested, Fig. 4 is according to constructed by the preferred embodiments of the present invention
The polarization curve of AB-Fe-N catalyst cyclical stabilities, as shown in figure 4, after by the cyclic voltammetric of 5000 circles in oxygen,
We conducted ORR test, catalyst of the invention also show good stability, and carrying current and half wave potential exist
After the circle of circulation 5000, almost without any decay, so the catalyst of single atomic dispersion has very for commercialized application
Big potentiality.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all any modification, equivalent and improvement made within the spirit and principles of the invention etc., all should be included
Within protection scope of the present invention.
Claims (7)
1. a kind of atom level disperses the preparation method of non-noble metal fuel cell cathod catalyst, it is characterised in that this method bag
Include the following steps：
(a) it is alginate solution to dissolve by heating alginate, keeps the heating-up temperature and in the alginate solution
Metal salt is added, thus generates alginate chelate solution；
(b) organic nitrogen compound is added in the alginate chelate solution as made from step (a), after the two reacts and will reacted
Product be evaporated to obtain powdered compounds；
(c) powdered compounds are carried out with first time heat treatment, pickling successively and is heat-treated for second, is thus made required
Catalyst.
2. a kind of atom level as claimed in claim 1 disperses the preparation method of non-noble metal fuel cell cathod catalyst, its
It is characterised by, in step (a), the mol ratio of the alginate and metal salt is 1/4~16:1.
3. a kind of atom level as claimed in claim 1 or 2 disperses the preparation method of non-noble metal fuel cell cathod catalyst,
Characterized in that, in step (a), the temperature range of the heating is 30 DEG C~100 DEG C.
4. a kind of atom level as described in claim any one of 1-3 disperses the preparation of non-noble metal fuel cell cathod catalyst
Method, it is characterised in that in step (a), the metal salt uses FeCl3、Fe(NO3)3、Fe(CH3COO)2、NiCl2Or Co
(NO3)3In one kind or combination.
5. a kind of atom level as described in claim any one of 1-4 disperses the preparation of non-noble metal fuel cell cathod catalyst
Method, it is characterised in that in step (b), the organic nitrogen compound of addition is 1~32 with the mol ratio of the metal salt:
1。
6. a kind of atom level as described in claim any one of 1-5 disperses the preparation of non-noble metal fuel cell cathod catalyst
Method, it is characterised in that in step (b), the organic nitrogen compound is in ethylenediamine, melamine, cyanamide or dicyandiamide
A kind of or combination.
7. a kind of atom level as described in claim any one of 1-6 disperses the preparation of non-noble metal fuel cell cathod catalyst
Method, it is characterised in that in step (c), the first time and second of heat treatment temperature are 300 DEG C~1200 DEG C, are protected
The warm time is 0.5h~12h.
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| CN109119649B (en) * | 2018-08-31 | 2021-08-31 | 广东工业大学 | Cobalt monoatomic catalyst with cobalt atoms anchored on carbon nanofibers and preparation method and application thereof |
| CN110201702A (en) * | 2019-06-14 | 2019-09-06 | 北京大学深圳研究生院 | Carbon carries the nitrogenous compound oxygen reduction catalyst preparation method of monoatomic metal and gained catalyst |
| CN110336044A (en) * | 2019-06-17 | 2019-10-15 | 华中科技大学 | A kind of monatomic fuel battery cathod catalyst of base metal, its preparation and application |
| CN112808289A (en) * | 2020-12-31 | 2021-05-18 | 杭州师范大学 | Alginate-based metal monatomic catalyst and preparation method and application thereof |
| CN113634287A (en) * | 2021-08-10 | 2021-11-12 | 复旦大学 | Metal atom loaded nitrogen-doped porous carbon material and super-assembly preparation method thereof |
| CN113937307A (en) * | 2021-09-10 | 2022-01-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
| CN113937307B (en) * | 2021-09-10 | 2023-03-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
| CN114243037A (en) * | 2021-12-06 | 2022-03-25 | 南京大学 | Metal nitrogen-carbon loaded low-platinum ordered alloy composite catalyst and preparation method thereof |
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