CN109755601A - A kind of hierarchical porous structure transition metal oxygen reduction catalyst and preparation method thereof - Google Patents
A kind of hierarchical porous structure transition metal oxygen reduction catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to inorganic advanced technical field of nano material, disclose a kind of hierarchical porous structure transition metal oxygen reduction catalyst and preparation method thereof, using powder carbon material as carrier, using zeolite imidazole organic framework growth in situ on powder carbon material surface as the presoma of catalyst；Then by the method for high temperature cabonization, the non noble metal oxygen reduction catalyst with abundant Co, N element and hierarchical porous structure is prepared；By the regulation to presoma thermal cracking temperature, the ratio and pore-size distribution of different elements in adjustable catalyst, and then control the oxygen reduction catalytic activity of catalyst.Catalytic performance of the invention has the characteristics that cheap, efficient close to business Pt/C (Pt content is 60%) catalyst；The introducing of carbon black reduces the particle size of catalyst, so that more active sites, which are exposed to surface, participates in reaction, while optimizes electronics and liquid phase transmittance process, therefore show excellent performance and application prospect in a fuel cell.
Description
Technical field
The invention belongs to inorganic advanced technical field of nano material, are to be related to a kind of fuel cell transition gold specifically
Belong to nanometer oxygen reduction catalyst and preparation method thereof.
Background technique
Hydrogen Energy is considered as the ideal energy of the 21 century mankind, and fuel cell is a kind of height for converting Hydrogen Energy to electric energy
Imitate energy conversion device.Therefore develop fuel cell technology, have for energy sustainable development and building Hydrogen Energy society important
Meaning.However the valuableness of conventional precious metal catalyst, limit the further development of fuel cell.To reduce fuel cell production
Cost pushes the commercial applications of fuel cell, the emphasis for being developed into researcher's concern of non noble metal oxygen reduction catalyst.
However, being mostly focused in the theoretical research of catalyst for the exploration of oxygen reduction catalyst at present, for actual fuel cell
The Catalyst Design and research work that application environment carries out are less.
In numerous catalysis materials, zeolite imidazole frame (ZIF) catalyst is because of its content of heteroatoms abundant and unique
Dodecahedron pattern has attracted the concern of researcher.By the carbonization treatment to ZIF presoma, researcher is prepared for having sky
The Co base oxygen reduction catalyst of core structure.In rotating disk electrode (r.d.e) test, which shows good hydrogen reduction performance
(half wave potential is about 0.87V vs RHE, 0.1M KOH).But since that there is particle diameters is excessive (about for this catalyst
For 1500nm) and the problem of be hollow structure, therefore its electric conductivity and mechanicalness are not able to satisfy the requirement of fuel cells applications.Pass through
The catalyst particle that traditional adsorption method is prepared on carbon black, no doubt it is conductive can, but because suction-operated is weaker, miscellaneous original
Sub- content is extremely low, and general oxygen reduction activity is only shown in alkaline solution, does not have universality.At the same time, researcher
The ZIF catalyst of growth in situ is also synthesized using foam dopamine as substrate, the catalyst surface of synthesis has a large amount of carbon nanometers
Pipe structure shows preferable oxygen reduction activity (starting voltage 0.91V vs RHE, 0.1M KOH).But because it is blocky knot
Structure needs further grinding just to can apply to fuel cell, increases operating procedure, be unfavorable for large-scale commercial applications application.
On the other hand, the manufacture craft of anionic membrane electrode also has the practical catalysis performance of the catalyst in the battery
Important influence.In recent years, FAA-3 (German FuMA-Tech) anion-exchange membrane is widely used in alkaline fuel cell
Membrane electrode research work.By optimization design, the monocell performance which makes can reach 223mW cm-2。
However, the Pt carrying capacity of its membrane electrode catalytic layer is about 0.8mg cm-2, the use of a large amount of noble metals increases the production of membrane electrode
Cost brings difficulty for commercial applications.Therefore, there is researcher using Fe/Co-N non-precious metal catalyst instead of traditional Pt/
C catalyst is applied to alkaline fuel cell, does not obtain performance (the 35mW cm for being similar to business Pt/C but-2).This also reflects
There is the phenomenon that disconnecting between current Catalyst Design and fuel cells applications, therefore based on actual fuel cell test
Catalyst Design, be the current unavoidable problem of catalyst field research.In addition, researcher is also based on day Bender mountain company
Anion-exchange membrane (#A201) made the base metal alkalinity membrane electrode that cathode is Co/N/MWCNT catalyst, and obtain
Preferable battery performance (~120mW cm-2), show application tool of the basic catalyst in anion-exchange membrane fuel cells
There is certain prospect.
Summary of the invention
The present invention is to solve at high cost present in fuel cell production, activity is low and Catalyst Design loses contact with reality
Etc. technical problems, be designed based on alkaline fuel cell actual conditions, propose a kind of hierarchical porous structure oxo transition metal also
Raw catalyst and preparation method thereof, this method uses cheap chemicals as raw material, by the side for standing growth and high temperature cabonization
Method, which has been prepared, has micropore abundant, mesoporous and macroporous structure, and good conductivity, the high oxygen reduction catalyst of activity, catalysis
It is active controllable, it is easy to amplify, and applied raw to reduce fuel cell in the membrane electrode preparation process of alkaline fuel cell
Cost is produced, thus there is important practical application meaning and economic benefit.
In order to solve the above-mentioned technical problem, the present invention is achieved by technical solution below:
A kind of hierarchical porous structure transition metal oxygen reduction catalyst, is obtained by following preparation method:
(1) by the mistake of the powder carbon material of 1 part of mass parts, the polyvinylpyrrolidone of 1 part of mass parts and 3 parts of mass parts
It crosses metal salt to be dispersed in dispersant nonpolar liquid, ultrasonic disperse is to uniform；
(2) 2-methylimidazole of 4 parts of mass parts is dispersed in and step (1) equal volume, another polarity of the same race point
In dispersion liquid, ultrasonic disperse is to uniform；
(3) mixed liquor that step (1) obtains is stirred evenly in -5~5 DEG C of environment, then rapidly obtains step (2)
The mixed liquor obtained pours into wherein, continues stirring in identical environment 10~60 minutes；Then the mixed liquor stirred evenly is existed
24~72 hours are stood in room temperature environment；
(4) mixed liquor after standing is centrifugated, washing is multiple；It is then that the black solid cleaned up is sufficiently dry
It is dry, that is, obtain catalyst precursor；
(5) catalyst precursor is heated to 600~800 under inertia or mixed atmosphere with the rate of 3~10 DEG C/min
DEG C, constant temperature 1~4 hour, it is then naturally cooling to room temperature, i.e. acquisition carbonized product；
(6) resulting carbonized product is cleaned using acid solution, removes extra metallic particles, centrifuge separation is consolidated
Body, and sufficiently drying obtains final oxygen reduction catalyst by it.
Further, powder carbon material described in step (1) is carbon black, in graphene, carbon nanotube, graphite powder
It is a kind of.
Further, transition metal salt described in step (1) is cabaltous nitrate hexahydrate, green vitriol, six water
Close one of zinc nitrate.
Further, dispersant nonpolar liquid described in step (1) is one kind of methanol, ethyl alcohol, water.
Further, the dosage of dispersant nonpolar liquid described in step (1) is 20~100mL.
Further, the drying temperature in step (4) is 60~80 DEG C.
Further, the inert atmosphere in step (5) includes nitrogen, argon gas, helium and one of hydrogen-argon-mixed.
Further, the pH value of the acid solution in step (6) is 0~1.
A kind of preparation method of the hierarchical porous structure transition metal oxygen reduction catalyst, this method according to the following steps into
Row:
(1) by the mistake of the powder carbon material of 1 part of mass parts, the polyvinylpyrrolidone of 1 part of mass parts and 3 parts of mass parts
It crosses metal salt to be dispersed in dispersant nonpolar liquid, ultrasonic disperse is to uniform；
(2) 2-methylimidazole of 4 parts of mass parts is dispersed in and step (1) equal volume, another polarity of the same race point
In dispersion liquid, ultrasonic disperse is to uniform；
(3) mixed liquor that step (1) obtains is stirred evenly in -5~5 DEG C of environment, then rapidly obtains step (2)
The mixed liquor obtained pours into wherein, continues stirring in identical environment 10~60 minutes；Then the mixed liquor stirred evenly is existed
24~72 hours are stood in room temperature environment；
(4) mixed liquor after standing is centrifugated, washing is multiple；It is then that the black solid cleaned up is sufficiently dry
It is dry, that is, obtain catalyst precursor；
(5) catalyst precursor is heated to 600~800 under inertia or mixed atmosphere with the rate of 3~10 DEG C/min
DEG C, constant temperature 1~4 hour, it is then naturally cooling to room temperature, i.e. acquisition carbonized product；
(6) resulting carbonized product is cleaned using acid solution, removes extra metallic particles, centrifuge separation is consolidated
Body, and sufficiently drying obtains final oxygen reduction catalyst by it.
The beneficial effects of the present invention are:
The present invention in the process wants electric conductivity and active sites for battery testing based on the actual conditions of fuel cell
It asks, by being adsorbed in the powder carbon material surface for having wrapped up polyvinylpyrrolidone, growing zeolite imidazole organic frame (ZIF)
Mode is prepared for the presoma of the catalyst；Then at a lower temperature, carbonization treatment is carried out to the presoma, in this mistake
Cheng Zhong, powder carbon material provide biggish specific surface area for the growth of ZIF, promote the dispersion of ZIF particle and subtracting for size
It is small；Simultaneously as the high conductivity of carbon material itself, drops the carburizing temperature in the catalyst preparation process further
It is low, while retaining hetero atom (Co, Fe, N atom) to greatest extent, improve active sites (CoNx、FeNx) quantity, and
The intrinsic microcellular structure of ZIF material is remained, hierarchical porous structure is formd.Finally, the catalyst is in offline and on-line performance table
In sign, the performance close to business Pt/C is shown.In addition to this, raw material used in catalyst prepared by the present invention is honest and clean
Valence chemicals, relative to conventional precious metal oxygen reduction catalyst, the cost sharp fall of the catalyst.Therefore the material at
This and aspect of performance have dual advantage.In fuel cell actual application, which can replace your traditional gold
Metal catalyst reduces membrane electrode cost of manufacture as cathode catalysis layer material, promotes the commercial applications of fuel cell.
Detailed description of the invention
Fig. 1 is zeolite imidazole frame-carbon black composite material scanning electron microscope (SEM) photograph prepared by embodiment 1；
Fig. 2 is that zeolite imidazole frame prepared by embodiment 1-carbon black composite material particle diameter distribution statistics and Gauss curve fitting are bent
Line chart；
Fig. 3 is transition metal oxygen reduction catalyst scanning electron microscope (SEM) photograph prepared by embodiment 1；
Fig. 4 is hydrogen reduction performance chart of the transition-metal catalyst in 0.1M KOH prepared by embodiment 1；
Fig. 5 is performance chart of the transition-metal catalyst in alkaline fuel cell prepared by embodiment 1；
Fig. 6 is zeolite imidazole frame material scanning electron microscope (SEM) photograph traditional prepared by comparative example 1.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, and following embodiment can make this profession
The present invention, but do not limit the invention in any way is more completely understood in technical staff.
Embodiment 1
(1) 500mg commercial carbon blacks, 1.5g cabaltous nitrate hexahydrate and 500mg polyvinylpyrrolidone are dispersed in 40mL first
In alcohol, ultrasonic 15min makes carbon black, cobalt nitrate and polyvinylpyrrolidone be uniformly dispersed, and obtains black suspension (mixture A)；
(2) 2g 2-methylimidazole is dispersed in another 40mL methanol, ultrasonic 5min obtains the solution of clear
(mixture B)；
(3) mixture A is placed in 0 DEG C of environment, magnetic agitation, 30min is carried out with the speed of 600rpm；It then will mixing
Object B is quickly poured into mixture A, continues to stir 40min in 0 DEG C of environment；
(4) stop stirring after 40min, take out magneton, be stored at room temperature after sealing 72 hours；
(5) sample after standing is centrifugated, obtains solid with ultrapure water 2 times, finally, centrifuge separation, takes out
Solid is the presoma of catalyst, is placed it in 60 DEG C of air dry ovens, 12 hours dry, spare；
(6) catalyst precursor of acquisition is placed in quartz boat, under an argon atmosphere, with the heating rate of 5 DEG C/min
Rise to 700 DEG C, and constant temperature 2 hours；Then it is naturally cooling to room temperature；
(7) sample after taking-up high-temperature process, uses 0.1M HClO4Pickling is carried out to it, using magnetic agitation,
It is stirred 12 hours under 300rpm revolving speed；
(8) centrifuge separation obtains solid, and twice using ultrapure water cleaning, is isolating solid matter, placing it in 60
It is 12 hours dry in DEG C air dry oven, as transition metal oxygen reduction catalyst.
Fig. 1 is the zeolite imidazole frame-carbon black composite material scanning electron microscope (SEM) photograph prepared, which clearly reflects
The pattern of catalyst precursor, i.e., centered on carbon black, zeolite imidazole frame is wrapped up in surrounding to be grown, and forms zeolite imidazole frame-
Carbon black composite material.By for statistical analysis to particle size in SEM figure, it is known that its particle size is about 150nm, such as Fig. 2.
After high temperature cabonization, huge variation, such as Fig. 3 is had occurred in catalyst morphology, and dodecahedron pattern disappears, and carbon blacksurface produces
Raw a large amount of folds form micropore, mesoporous, macropore composition hierarchical porous structure, these ducts are also in oxygen reduction activity simultaneously
The heart promotes reaction and mass transport process, improves catalytic activity.
For the hydrogen reduction catalytic effect for verifying above-mentioned catalyst, also to the catalyst carried out rotating disk electrode (r.d.e) test and
Fuel-cell single-cell test, the specific steps are as follows:
1. rotating disk electrode (r.d.e) is tested:
(1) oxygen reduction catalyst made from 5mg obtained in the present embodiment is dispersed in 1mL isopropyl alcohol and water (quality point
Number is 75% isopropanol and 25% water) mixed solution in, ultrasound 10 minutes；
(2) 40 μ L FAA-3 coating solutions are added, continue ultrasound 60 minutes, it is not high which is always maintained at ultrasonic water bath temperature
In 30 DEG C, ultrasound terminates to obtain catalyst ink；
(3) take 15 μ L catalyst ink water droplets in rotating disk electrode (r.d.e), naturally dry obtains working electrode；
(4) electrode system is used, in five mouthfuls of flasks, hydrogen reduction performance is carried out to the working electrode under 0.1M KOH system
It tests, in test process, guarantees that oxygen is passed through solution system with the flow velocity of 50mL/min；
(5) linear voltammetric scan method is used, scanning range is 1.0~0.2V (relative to reversible hydrogen electrode), scanning speed
Degree is 5mV/s.
2. fuel-cell single-cell is tested:
(1) Pt/C for being 60% by 8 milligrams of Co base catalyst obtained in the present embodiment and 2.67 milligrams of Pt mass fractions
Catalyst is dispersed in the mixed solution of 1.5mL isopropyl alcohol and water respectively (mass fraction is 75% isopropanol and 25% water)
In, ultrasound 10 minutes；
(2) it is separately added into 320 μ L FAA-3 coating solutions into two solution, continues ultrasound 60 minutes, which protects always
Ultrasonic water bath temperature is held not higher than 30 DEG C, ultrasound terminates the catalyst ink for obtaining noble metal and transition metal；
(3) FAA-3-50 hydroxide ion exchange membrane is cut into the square sheets of 3cm × 3cm, and obtained Co is urged
Agent and Pt catalyst ink are sprayed at the cathode and anode of thin slice respectively, and spray area is controlled in 4cm2；
(4) membrane electrode prepared is immersed in 1M KOH 24 hours, then, being obtained for several times with ultrapure water can
Membrane electrode for fuel battery testing；
(5) by membrane electrode among fuel battery double plates, apply the pretightning force of 4N m, hydrogen and oxygen are drawn respectively
Enter the anode and cathode of fuel cell and is tested under 40 DEG C, 80% relative humidity.
Rotating disk electrode (r.d.e) test and fuel-cell single-cell test have respectively represented the research of catalyst theoretical performance and have urged
Agent actual performance research.It is found as shown in figure 4, being tested by rotating disk electrode (r.d.e), in 0.1M KOH solution, the catalyst
Open-circuit voltage is about 0.96V, and carrying current is about 5mA cm-2(at 1600 rpm), should the result shows that, this oxo transition metal
Reducing catalyst has the ability of preferable catalytic oxidation-reduction reaction.
In order to further confirm the practical application effect of the catalyst, fuel-cell single-cell performance test has also been carried out.
As shown in Figure 5 the experiment has found that the maximum power density of the membrane electrode of transition-metal catalyst preparation is about 95mW cm-2, reach
It is horizontal to transition-metal catalyst industry-leading, to prove that the catalyst has very strong commercial application prospect.
Embodiment 2
(1) 500mg graphene, 1.5g green vitriol and 500mg polyvinylpyrrolidone are dispersed in 20mL second
In alcohol, ultrasonic 15min makes graphene, green vitriol and polyvinylpyrrolidone be uniformly dispersed, and obtains black suspension
(mixture A)；
(2) 2g 2-methylimidazole is dispersed in another 20mL ethyl alcohol, ultrasonic 5min obtains the solution of clear
(mixture B)；
(3) mixture A is placed in -5 DEG C of environment, magnetic agitation 30min is carried out with the speed of 600rpm；It then will mixing
Object B is quickly poured into mixture A, continues to stir 10min in -5 DEG C of environment；
(4) stop stirring after 10min, take out magneton, be stored at room temperature after sealing 24 hours；
(5) sample after standing is centrifugated, obtains solid with ultrapure water 2 times, finally, centrifuge separation, takes out
Solid is the presoma of catalyst, is placed it in 70 DEG C of air dry ovens, 12 hours dry, spare；
(6) catalyst precursor of acquisition is placed in quartz boat, in a nitrogen atmosphere, with the heating rate of 3 DEG C/min
Rise to 600 DEG C, and constant temperature 1 hour；Then it is naturally cooling to room temperature；
(7) sample after taking-up high-temperature process, uses 1M HClO4(pH value 0) carries out pickling to it, is stirred using magnetic force
It mixes, is stirred 12 hours under 300rpm revolving speed；
(8) centrifuge separation obtains solid, and twice using ultrapure water cleaning, is isolating solid matter, placing it in 70
It is 12 hours dry in DEG C air dry oven, as transition metal oxygen reduction catalyst.
For the hydrogen reduction catalytic effect for verifying above-mentioned catalyst, also to the catalyst carried out rotating disk electrode (r.d.e) test and
Fuel-cell single-cell test, specific steps are identical with the testing procedure in embodiment 1.
Through this embodiment, Fe base ZIF presoma is successfully prepared, and the method by being carbonized prepares the gold of transition containing Fe
Belong to oxygen reduction catalyst.With the reduction of carburizing temperature and the shortening of carbonization time, Fe transition metal prepared by the present embodiment
Oxygen reduction catalyst contains more hetero atoms and microcellular structure abundant, these structures are typically considered oxygen reduction reaction
Activated centre, therefore the catalyst has preferable intrinsic catalytic activity.But due to the reduction of degree of graphitization, the catalyst
Electric conductivity existing defects, for catalyst prepared in embodiment 1, the electric conductivity of the catalyst is slightly decreased.
Embodiment 3
(1) 500mg carbon nanotube, 1.5g zinc nitrate hexahydrate and 500mg polyvinylpyrrolidone are dispersed in 100mL second
In alcohol, ultrasonic 15min makes carbon nanotube, zinc nitrate hexahydrate and polyvinylpyrrolidone be uniformly dispersed, and obtains black suspension
(mixture A)；
(2) 2g 2-methylimidazole is dispersed in another 100mL ethyl alcohol, ultrasonic 5min obtains the solution of clear
(mixture B)；
(3) mixture A is placed in 5 DEG C of environment, magnetic agitation 30min is carried out with the speed of 600rpm；It then will mixing
Object B is quickly poured into mixture A, continues to stir 60min in 5 DEG C of environment；
(4) stop stirring after 60min, take out magneton, be stored at room temperature after sealing 48 hours；
(5) sample after standing is centrifugated, obtains solid with ultrapure water 2 times, finally, centrifuge separation, takes out
Solid is the presoma of catalyst, is placed it in 80 DEG C of air dry ovens, 12 hours dry, spare；
(6) catalyst precursor of acquisition is placed in quartz boat, under helium atmosphere, with the heating rate of 10 DEG C/min
Rise to 800 DEG C, and constant temperature 4 hours；Then it is naturally cooling to room temperature；
(7) sample after taking-up high-temperature process, uses 0.1M HClO4(pH value 1) carries out pickling to it, uses magnetic force
Stirring, is stirred 12 hours under 300rpm revolving speed；
(8) centrifuge separation obtains solid, and twice using ultrapure water cleaning, is isolating solid matter, placing it in 80
It is 12 hours dry in DEG C air dry oven, as transition metal oxygen reduction catalyst.
For the hydrogen reduction catalytic effect for verifying above-mentioned catalyst, also to the catalyst carried out rotating disk electrode (r.d.e) test and
Fuel-cell single-cell test, specific steps are identical with the testing procedure in embodiment 1.
The non noble metal oxygen reduction catalyst that Zn-ZIF presoma is derived can be prepared through this embodiment, due to
The fusing point of metallic zinc is 419.5 DEG C, therefore Zn ion can be reduced into metallic zinc during the high temperature treatment process, with carburizing temperature
Raising, metallic zinc will further melt, finally be taken out of by inert gas.Accordingly, with respect to other embodiments, this method is made
The standby oxygen reduction catalyst come out is free of nano-metal particle.But since metal Zn high-temperature gasification acts on, so that catalyst surface
With micropore more abundant and meso-hole structure, the presence of these structures increases the effective active area of catalyst, promotes
Liquid phase mass transport process is conducive to the raising of catalytic activity.
Embodiment 4
(1) 500mg graphite powder, 1.5g cabaltous nitrate hexahydrate and 500mg polyvinylpyrrolidone are dispersed in 50mL methanol
In, ultrasonic 15min makes graphite powder, cabaltous nitrate hexahydrate and polyvinylpyrrolidone be uniformly dispersed, and it is (mixed to obtain black suspension
Close object A)；
(2) 2g 2-methylimidazole is dispersed in another 50mL methanol, ultrasonic 5min obtains the solution of clear
(mixture B)；
(3) mixture A is placed in 5 DEG C of environment, magnetic agitation 30min is carried out with the speed of 600rpm；It then will mixing
Object B is quickly poured into mixture A, continues to stir 10min in 5 DEG C of environment；
(4) stop stirring after 10min, take out magneton, be stored at room temperature after sealing 72 hours；
(5) sample after standing is centrifugated, obtains solid with ultrapure water 2 times, finally, centrifuge separation, takes out
Solid is the presoma of catalyst, is placed it in 65 DEG C of air dry ovens, 12 hours dry, spare；
(6) catalyst precursor of acquisition is placed in quartz boat, under hydrogen-argon-mixed atmosphere, with the liter of 6 DEG C/min
Warm rate rises to 650 DEG C, and constant temperature 1.5 hours；Then it is naturally cooling to room temperature；
(7) sample after taking-up high-temperature process, uses 0.5M HClO4Pickling is carried out to it, using magnetic agitation,
It is stirred 12 hours under 300rpm revolving speed；
(8) centrifuge separation obtains solid, and twice using ultrapure water cleaning, is isolating solid matter, placing it in 65
It is 12 hours dry in DEG C air dry oven, as transition metal oxygen reduction catalyst.
For the hydrogen reduction catalytic effect for verifying above-mentioned catalyst, also to the catalyst carried out rotating disk electrode (r.d.e) test and
Fuel-cell single-cell test, specific steps are identical with the testing procedure in embodiment 1.
The embodiment is prepared for transition metal oxygen reduction catalyst derived from Co base ZIF structure.Before adjusting catalyst
The growth temperature for driving body, can regulate and control the partial size of catalyst precursor.Precursor mother liquor temperature rises to 5 by 0 DEG C
DEG C when, grown by 72 hours standings, which further grows up.Simultaneously as the increase of ZIF particle size, preceding
Co, N element ratio in body is driven further to increase.By in hydrogen-argon-mixed high temperature carbonization treatment, the Heteroatom dopings such as Co, N
Into in carbon structure, more active sites are formed, are conducive to the raising of catalyst activity.On the other hand, since pyrolytic process is also
It is carried out under originality atmosphere, therefore more Co elements are reduced into metallic state, and are removed in pickling later, are conducive to
The raising of catalyst mass activity.
Embodiment 5
(1) 500mg carbon black, 1.5g cabaltous nitrate hexahydrate and 500mg polyvinylpyrrolidone are dispersed in 50mL water, are surpassed
Sound 15min makes carbon black, cabaltous nitrate hexahydrate and polyvinylpyrrolidone be uniformly dispersed, and obtains black suspension (mixture A)；
(2) 2g 2-methylimidazole is dispersed in another 50mL water, ultrasonic 5min, the solution for obtaining clear is (mixed
Close object B)；
(3) mixture A is placed in 5 DEG C of environment, magnetic agitation 30min is carried out with the speed of 600rpm；It then will mixing
Object B is quickly poured into mixture A, continues to stir 20min in 5 DEG C of environment；
(4) stop stirring after 20min, take out magneton, be stored at room temperature after sealing 72 hours；
(5) sample after standing is centrifugated, obtains solid with ultrapure water 2 times, finally, centrifuge separation, takes out
Solid is the presoma of catalyst, is placed it in 70 DEG C of air dry ovens, 12 hours dry, spare；
(6) catalyst precursor of acquisition is placed in quartz boat, under an argon atmosphere, with the heating rate of 4 DEG C/min
Rise to 800 DEG C, and constant temperature 3 hours；Then it is naturally cooling to room temperature；
(7) sample after taking-up high-temperature process, uses 0.1M HClO4Pickling is carried out to it, using magnetic agitation,
It is stirred 12 hours under 300rpm revolving speed；
(8) centrifuge separation obtains solid, and twice using ultrapure water cleaning, is isolating solid matter, placing it in 70
It is 12 hours dry in DEG C air dry oven, as transition metal oxygen reduction catalyst.
For the hydrogen reduction catalytic effect for verifying above-mentioned catalyst, also to the catalyst carried out rotating disk electrode (r.d.e) test and
Fuel-cell single-cell test, specific steps are identical with the testing procedure in embodiment 1.
By in this present embodiment, catalyst precursor synthesizes in water, relative to embodiment 1, the price of aqueous solvent
It is relatively low, it is environmental-friendly, it is a kind of more cheap, environmental protection reagent.Aqueous solution plays the role of promotion to the growth of ZIF, makes
It is larger to obtain catalyst precursor particles size.This is conducive to more Co, N hetero atoms and is introduced in above carbon black-supported, improves
Doping level, is conducive to the promotion of catalyst activity bit quantity.
Comparative example 1
(1) 1.5g cabaltous nitrate hexahydrate is dispersed in 50mL methanol, ultrasonic 15min, keeps cabaltous nitrate hexahydrate dispersion equal
It is even, it obtains red clear solution (mixture A)；
(2) 2g 2-methylimidazole is dispersed in another 50mL water, ultrasonic 5min, the solution for obtaining clear is (mixed
Close object B)；
(3) mixture B is quickly poured into mixture A, is stored at room temperature after sealing 72 hours；
(5) sample after standing is centrifugated, obtains solid with ultrapure water 2 times, finally, centrifuge separation, takes out
Solid is the presoma of catalyst, is placed it in 70 DEG C of air dry ovens, 12 hours dry, spare；
(6) catalyst precursor of acquisition is placed in quartz boat, under an argon atmosphere, with the heating rate of 5 DEG C/min
Rise to 700 DEG C, and constant temperature 2 hours；Then it is naturally cooling to room temperature；
(7) sample after taking-up high-temperature process, uses 0.1M HClO4Pickling is carried out to it, using magnetic agitation,
It is stirred 12 hours under 300rpm revolving speed；
(8) centrifuge separation obtains solid, and twice using ultrapure water cleaning, is isolating solid matter, placing it in 70
It is 12 hours dry in DEG C air dry oven, as transition metal oxygen reduction catalyst.
This comparative example is the transition metal oxygen reduction catalyst that a kind of ZIF prepared using traditional method is derived,
Compared to the present invention, it is maximum the difference is that, do not use conductive powder carbon material as substrate in this comparative example.
Therefore, ZIF particle agglomeration, formation diameter in the catalyst precursor particles of 500nm, such as Fig. 6, can about pass through in mother liquor
It crosses after carbonization, forms blocky hollow structure.This structure can make fuel cell catalyst layer three phase boundary area reduce, gas-liquid
Mass transport process and electron transfer process are obstructed, and finally make fuel battery performance poor.By this comparative example, further illustrate
Catalyst prepared by the present invention has better catalytic effect and fuel cell actual application prospect.
Although the preferred embodiment of the present invention is described above in conjunction with attached drawing, the invention is not limited to upper
The specific embodiment stated, the above mentioned embodiment is only schematical, be not it is restrictive, this field it is common
Technical staff under the inspiration of the present invention, without breaking away from the scope protected by the purposes and claims of the present invention, may be used also
By make it is many in the form of specific transformation, within these are all belonged to the scope of protection of the present invention.
Claims (9)
1. a kind of hierarchical porous structure transition metal oxygen reduction catalyst, which is characterized in that obtained by following preparation method:
(1) by the transition gold of the powder carbon material of 1 part of mass parts, the polyvinylpyrrolidone of 1 part of mass parts and 3 parts of mass parts
Belong to salt to be dispersed in dispersant nonpolar liquid, ultrasonic disperse is to uniform；
(2) 2-methylimidazole of 4 parts of mass parts is dispersed in and step (1) equal volume, another dispersant nonpolar liquid of the same race
In, ultrasonic disperse is to uniform；
(3) mixed liquor that step (1) obtains is stirred evenly in -5~5 DEG C of environment, then rapidly obtains step (2)
Mixed liquor pours into wherein, continues stirring in identical environment 10~60 minutes；Then by the mixed liquor stirred evenly in room temperature
24~72 hours are stood in environment；
(4) mixed liquor after standing is centrifugated, washing is multiple；It is then that the black solid cleaned up is sufficiently dry, i.e.,
Obtain catalyst precursor；
(5) catalyst precursor is heated to 600~800 DEG C under inertia or mixed atmosphere with the rate of 3~10 DEG C/min, perseverance
Temperature 1~4 hour, is then naturally cooling to room temperature, i.e. acquisition carbonized product；
(6) resulting carbonized product to be cleaned using acid solution, removes extra metallic particles, centrifuge separation obtains solid, and
By it, sufficiently drying obtains final oxygen reduction catalyst.
2. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(1) powder carbon material described in is one of carbon black, graphene, carbon nanotube, graphite powder.
3. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(1) transition metal salt described in is one of cabaltous nitrate hexahydrate, green vitriol, zinc nitrate hexahydrate.
4. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(1) dispersant nonpolar liquid described in is one kind of methanol, ethyl alcohol, water.
5. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(1) dosage of the dispersant nonpolar liquid described in is 20~100mL.
6. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(4) drying temperature in is 60~80 DEG C.
7. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(5) inert atmosphere in includes nitrogen, argon gas, helium and one of hydrogen-argon-mixed.
8. a kind of hierarchical porous structure transition metal oxygen reduction catalyst according to claim 1, which is characterized in that step
(6) pH value of the acid solution in is 0~1.
9. a kind of preparation method of the hierarchical porous structure transition metal oxygen reduction catalyst as described in any one of claim 1-8,
It is characterized in that, this method follows the steps below:
(1) by the transition gold of the powder carbon material of 1 part of mass parts, the polyvinylpyrrolidone of 1 part of mass parts and 3 parts of mass parts
Belong to salt to be dispersed in dispersant nonpolar liquid, ultrasonic disperse is to uniform；
(2) 2-methylimidazole of 4 parts of mass parts is dispersed in and step (1) equal volume, another dispersant nonpolar liquid of the same race
In, ultrasonic disperse is to uniform；
(3) mixed liquor that step (1) obtains is stirred evenly in -5~5 DEG C of environment, then rapidly obtains step (2)
Mixed liquor pours into wherein, continues stirring in identical environment 10~60 minutes；Then by the mixed liquor stirred evenly in room temperature
24~72 hours are stood in environment；
(4) mixed liquor after standing is centrifugated, washing is multiple；It is then that the black solid cleaned up is sufficiently dry, i.e.,
Obtain catalyst precursor；
(5) catalyst precursor is heated to 600~800 DEG C under inertia or mixed atmosphere with the rate of 3~10 DEG C/min, perseverance
Temperature 1~4 hour, is then naturally cooling to room temperature, i.e. acquisition carbonized product；
(6) resulting carbonized product to be cleaned using acid solution, removes extra metallic particles, centrifuge separation obtains solid, and
By it, sufficiently drying obtains final oxygen reduction catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649275A (en) * | 2019-09-25 | 2020-01-03 | 三峡大学 | Co2Preparation method of P/NPC electrocatalyst |
| CN111430733A (en) * | 2020-03-17 | 2020-07-17 | 上海电气集团股份有限公司 | Non-noble metal oxygen reduction catalyst for fuel cell 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 |
| CN113764690A (en) * | 2021-09-02 | 2021-12-07 | 中汽创智科技有限公司 | Composite catalyst and preparation method and application thereof |
| CN113813975A (en) * | 2021-07-30 | 2021-12-21 | 五邑大学 | ZIF-8 derived hierarchical pore M-N-C catalyst and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150295248A1 (en) * | 2011-06-15 | 2015-10-15 | Stc.Unm | Cathode catalysts for fuel cell application derived from polymer precursors |
| CN105289695A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | Graphene loaded Co-N-C oxygen reduction catalyst and preparation method thereof |
| CN106549163A (en) * | 2016-11-03 | 2017-03-29 | 大连理工大学 | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate |
| US9722256B1 (en) * | 2012-11-27 | 2017-08-01 | Stc.Unm | Imidazole-derived materials |
| CN107069048A (en) * | 2017-03-14 | 2017-08-18 | 中南大学 | A kind of preparation method of Fe N C oxygen reduction catalysts |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
| CN108598504A (en) * | 2018-04-19 | 2018-09-28 | 燕山大学 | A kind of high catalytic activity fuel battery cathod catalyst |
| CN109078501A (en) * | 2018-07-11 | 2018-12-25 | 天津大学 | A kind of preparation method of the amberplex with orderly ion conduction structure |
| CN109248702A (en) * | 2018-09-06 | 2019-01-22 | 北京科技大学 | The preparation method of the non-noble metal doped meso-porous carbon structure bifunctional electrocatalyst of N |
-
2019
- 2019-02-16 CN CN201910118357.2A patent/CN109755601A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150295248A1 (en) * | 2011-06-15 | 2015-10-15 | Stc.Unm | Cathode catalysts for fuel cell application derived from polymer precursors |
| US9722256B1 (en) * | 2012-11-27 | 2017-08-01 | Stc.Unm | Imidazole-derived materials |
| CN105289695A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | Graphene loaded Co-N-C oxygen reduction catalyst and preparation method thereof |
| CN106549163A (en) * | 2016-11-03 | 2017-03-29 | 大连理工大学 | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate |
| CN107069048A (en) * | 2017-03-14 | 2017-08-18 | 中南大学 | A kind of preparation method of Fe N C oxygen reduction catalysts |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
| CN108598504A (en) * | 2018-04-19 | 2018-09-28 | 燕山大学 | A kind of high catalytic activity fuel battery cathod catalyst |
| CN109078501A (en) * | 2018-07-11 | 2018-12-25 | 天津大学 | A kind of preparation method of the amberplex with orderly ion conduction structure |
| CN109248702A (en) * | 2018-09-06 | 2019-01-22 | 北京科技大学 | The preparation method of the non-noble metal doped meso-porous carbon structure bifunctional electrocatalyst of N |
Non-Patent Citations (3)
| Title |
|---|
| HAI-XIA ZHONG ET AL.: ""ZIF-8 Derived Graphene-Based Nitrogen-Doped Porous Carbon Sheets as Highly Efficient and Durable Oxygen Reduction Electrocatalysts"", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
| VANESSA ARMEL ET AL.: ""Effect of ZIF-8 Crystal Size on the O2 Electro-Reduction Performance of Pyrolyzed Fe-N-C Catalysts"", 《CATALYSTS》 * |
| 周学俊: ""M-Nx/C类非贵金属氧还原催化材料的构筑及其电化学性能研究"", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技I辑》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110649275A (en) * | 2019-09-25 | 2020-01-03 | 三峡大学 | Co2Preparation method of P/NPC electrocatalyst |
| CN110649275B (en) * | 2019-09-25 | 2022-04-08 | 三峡大学 | Co2Preparation method of P/NPC electrocatalyst |
| CN111430733A (en) * | 2020-03-17 | 2020-07-17 | 上海电气集团股份有限公司 | Non-noble metal oxygen reduction catalyst for fuel cell and preparation method thereof |
| CN111430733B (en) * | 2020-03-17 | 2022-09-20 | 上海电气集团股份有限公司 | Non-noble metal oxygen reduction catalyst for fuel cell 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 |
| CN113813975A (en) * | 2021-07-30 | 2021-12-21 | 五邑大学 | ZIF-8 derived hierarchical pore M-N-C catalyst and preparation method thereof |
| CN113764690A (en) * | 2021-09-02 | 2021-12-07 | 中汽创智科技有限公司 | Composite catalyst and preparation method and application thereof |
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