CN109301260A - A kind of biomass derived complex carbon material and its preparation method and application - Google Patents
A kind of biomass derived complex carbon material and its preparation method and application Download PDFInfo
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- CN109301260A CN109301260A CN201811265043.7A CN201811265043A CN109301260A CN 109301260 A CN109301260 A CN 109301260A CN 201811265043 A CN201811265043 A CN 201811265043A CN 109301260 A CN109301260 A CN 109301260A
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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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
- H01M4/9041—Metals or alloys
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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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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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
Abstract
The invention discloses a kind of biomass derived complex carbon materials and its preparation method and application, are related to catalysis material preparation field.The present invention specifically provides the derivative complex carbon material of a main laminaria, and using kelp as carbonaceous matrix, cobalt forms the composite construction with the carbon coating cobalt nano-particle of special core-shell structure by easy and green technology as compound particle.It, can be with the redox reaction of catalytic fuel cell cathode, catalytic activity, excellent methanol tolerance performance and long durability with higher using carbon-supported transition-metal catalyst made of the derivative complex carbon material of kelp provided by the invention.
Description
Technical field
The present invention relates to catalysis material preparation field more particularly to a kind of biomass derived complex carbon material and its preparation sides
Method and application.
Background technique
With the continuous consumption and concern of the whole world to environment of fossil fuel, to sustainable and the renewable sources of energy the explorations
Become one of current most important challenge.Currently, an important component of sustainable development chain be electrochemical storage and
Conversion equipment, such as fuel cell, photocatalytic water and solar battery etc..As a part of high-performance energy device, electro-catalysis
Agent plays important role in these electrochemical reactions.Currently, the elctro-catalyst largely used in practical applications is gold
Belong to platinum, but there are problems for metal platinum, for example, expensive, non-renewable, stability is poor, and anti methanol toxication ability is poor
Etc..Therefore, under study for action, it is desirable to find a kind of Cathodic oxygen reduction catalyst for substituting metal platinum.In recent years, it pursues high
Active, high durability is a research hotspot of electrochemical field without metal material or base metal base elctro-catalyst.Due to
The catalytic performance for being easy aggregation and your non-single transition metal of poorly conductive is generally poor.Although some transition metal elements are such as
Co, Fe and Mn have shown good electro catalytic activity, but their chemical stability is poor in practical application.In order to overcome
This obstacle, usually using carbon material as substrate in research, reason is that carbon material has stronger corrosion resistance, easily preparation and solely
Special surface property.Studies have shown that transition metal is loaded to the catalyst obtained in carbon substrate has excellent activity and stabilization
Property.This composite construction can prevent metallic particles from assembling, and further control the form and size of particle.Importantly, can
To promote the electric charge transfer at nanocarbon/metal interface, to improve electro catalytic activity.Currently, the carbon based metal of high activity, high stability
The design and synthesis of composite electrocatalyst are still a challenge.
Unquestionably, the Nature is a precious deposits abundant.It is that we provide natural resources abundant and unique
Structure.Compared with conventional energy resource, biomass resource has many advantages, such as environmentally friendly, widely available, renewable.Therefore, biology is provided
Source, which is converted into carbon material, becomes the hot spot studied now.Usual biomass derived carbon material has high-specific surface area, special hole knot
The features such as structure and Heteroatom doping.Some biomass contain certain groups, they can form complex with metal ion
Or the ability with physical absorption metal ion.Therefore, we can carry out carrying metal using biomass derived carbon as carrier
Particle shape is at a kind of composite catalyst.
Summary of the invention
The present invention specifically loads to cobalt nano-particle in carbon substrate, using kelp as carbonaceous matrix, by easy and green
Color technology forms the composite construction with the carbon coating cobalt nano-particle of special core-shell structure.Spread out using kelp provided by the invention
Carbon-supported transition-metal catalyst made of raw complex carbon material, can with the redox reaction of catalytic fuel cell cathode,
Catalytic activity, excellent methanol tolerance performance and long durability with higher.
It is an object of the present invention to provide a kind of material, the material is made after being calcined by the kelp for impregnating cobalt-carrying solution
?.
At least one of specifically, the material further includes following 1) -14) described:
1) calcining is calcined including 600 DEG C or more；
2) calcining includes calcining 1 hour or more；
3) calcining, which is included in nitrogen atmosphere, calcines；
4) it is 5-10 DEG C/min that the calcining, which includes heating rate,；
5) kelp includes dry kelp；
6) described impregnate includes the dry kelp of soaking 1g in every 50ml cobalt-carrying solution；
7) described impregnate includes being dipped to until kelp fully absorbs cobalt-carrying solution；
8) soaking includes soaking 6-12 hours；
9) cobalt-carrying solution includes the (NO containing Co3)2Aqueous solution；
10) cobalt-carrying solution includes that concentration of cobalt ions is 0.10M-1.0M in solution；
It 11) further include washing, dry kelp before the soaking；Specifically, the washing includes that deionized water is washed；Again
Specifically, the washing includes that deionized water is washed 3-5 times；Also specifically, washing 5 times；And/or the washing includes every 1g
Kelp is washed with 200ml deionization；And/or the drying includes 60-80 DEG C of drying, specifically, the drying include 60 DEG C,
70 DEG C or 80 DEG C of dryings；And/or the drying includes vacuum drying；And/or the drying includes drying 6-12 hours, specifically
, it is 6,8 or 12 hours dry；
It 12) further include rinsing, dry kelp after the soaking；Specifically, the rinsing includes that deionized water rinses；Again
Specifically, the washing includes that deionized water rinses 3-5 times；Also specifically, rinsing 3 times；And/or the rinsing includes every 1g
Kelp is rinsed with 200ml deionization；And/or the drying includes 60-80 DEG C of drying, specifically, the drying include 60 DEG C,
70 DEG C or 80 DEG C of dryings；And/or the drying includes vacuum drying；And/or the drying includes drying 6-12 hours, specifically
, it is 6,8 or 12 hours dry；
It 13) further include natural cooling after the calcining；
14) material includes calcined product graphitized carbon and cobalt nanometer particle.
At least one of again specifically, the material further includes following 1) -6) described:
1) calcining includes 650 DEG C~1000 DEG C calcinings；Specifically, 800 DEG C~1000 DEG C calcinings；Again specifically, 800
DEG C or 1000 DEG C calcining；
2) calcining includes calcining 2-3 hours；Specifically, calcining 2 hours；
3) it is 5 DEG C/min that the calcining, which includes heating rate,；
4) soaking includes soaking 12 hours；
5) cobalt-carrying solution includes that concentration of cobalt ions is 0.5M-1.0M in solution；Specifically, being 0.5M or 1.0M；
6) when the material includes calcined product graphitized carbon and cobalt nanometer particle, the material further includes nucleocapsid knot
Structure, the graphitized carbon coat cobalt nanometer particle；And/or the specific surface area of material is 147m2g-1, characteristic aperture 4nm；Specifically
, the partial size of the cobalt nanometer particle is between 5nm~20nm.
It is a further object to provide a kind of preparation methods of material, which comprises will impregnate containing cobalt
Up to the material after the kelp calcining of solution.
At least one of specifically, the method also includes following 1) -13) described:
1) calcining is calcined including 600 DEG C or more；
2) calcining includes calcining 1 hour or more；
3) calcining, which is included in nitrogen atmosphere, calcines；
4) it is 5-10 DEG C/min that the calcining, which includes heating rate,；
5) kelp includes dry kelp；
6) described impregnate includes the dry kelp of soaking 1g in every 50ml cobalt-carrying solution；
7) described impregnate includes being dipped to until kelp fully absorbs cobalt-carrying solution；
8) soaking includes soaking 6-12 hours；
9) cobalt-carrying solution includes the (NO containing Co3)2Aqueous solution；
10) cobalt-carrying solution includes that concentration of cobalt ions is 0.10M-1.0M in solution；
It 11) further include washing, dry kelp before the soaking；Specifically, the washing includes that deionized water is washed；Again
Specifically, the washing includes that deionized water is washed 3-5 times；Also specifically, washing 5 times；And/or the washing includes every 1g
Kelp is washed with 200ml deionization；And/or the drying includes 60-80 DEG C of drying；Specifically, the drying include 60 DEG C,
70 DEG C or 80 DEG C of dryings；And/or the drying includes vacuum drying；And/or the drying includes 6-12 hours dry；Specifically
, it is 6,8 or 12 hours dry；
It 12) further include rinsing, dry kelp after the soaking；Specifically, the rinsing includes that deionized water rinses；Again
Specifically, the washing includes that deionized water rinses 3-5 times；Also specifically, rinsing 3 times；And/or the rinsing includes every 1g
Kelp is rinsed with 200ml deionization；And/or the drying includes 60-80 DEG C of drying；Specifically, the drying include 60 DEG C,
70 DEG C or 80 DEG C of dryings；And/or the drying includes vacuum drying；And/or the drying includes 6-12 hours dry；Specifically
, it is 6,8 or 12 hours dry；
It 13) further include natural cooling after the calcining.
At least one of again specifically, the method also includes following 1) -5) described:
1) calcining includes 650 DEG C~1000 DEG C calcinings；Specifically, 800 DEG C~1000 DEG C calcinings；Again specifically, 800
DEG C or 1000 DEG C calcining；
2) calcining includes calcining 2-3 hours；Specifically, calcining 2 hours；
3) it is 5 DEG C/min that the calcining, which includes heating rate,；
4) soaking includes soaking 12 hours；
5) cobalt-carrying solution includes that concentration of cobalt ions is 0.5M-1.0M in solution；Specifically, being 0.5M or 1.0M.
It is also another object of the present invention to provide a kind of catalyst, the catalyst includes: by any material of the present invention
The material that the preparation method of material or any material of the present invention is directly prepared is dispersed in the mixed liquor of ethyl alcohol and naphthalene sweet smell
In, after ultrasound to obtain the final product.
Specifically, the ultrasound includes ultrasound 60 minutes；The volume ratio of the ethyl alcohol and naphthalene sweet smell is 24:1.
Of the invention a further object is provides a kind of preparation method of catalyst, which comprises appoints the present invention
Material that the preparation method of one material or any material of the present invention is directly prepared is dispersed in ethyl alcohol and naphthalene is fragrant
In mixed liquor, after ultrasound to obtain the final product.
Specifically, the ultrasound includes ultrasound 60 minutes；The volume ratio of the ethyl alcohol and naphthalene sweet smell is 24:1.
Of the invention a further object is provides the preparation side of any material of the present invention, any material of the present invention
The preparation method of material, any catalyst of the present invention or any catalyst of the present invention that method is directly prepared is straight
Connect the application for the catalyst being prepared.
Specifically, the application includes: the cathode material as fuel cell.
Of the invention a further object is that the preparation method for providing any material of the present invention or the present invention are any described
The application of the preparation method of catalyst.
Specifically, the application includes, the application in fuel cell or its Related product is being prepared.
Compared with the existing technology, the invention has the benefit that the multilayer stone of synthesis being composed of kelp and cobalt salt
Black carbon coating cobalt nano-particle is expected to the cathode material as fuel battery negative pole redox reaction.After optimizing carbonization temperature,
The sample of synthesis catalytic activity with higher, excellent methanol tolerance performance and long durability.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present application, constitutes part of this application, this Shen
Illustrative embodiments and their description please are not constituted an undue limitation on the present application for explaining the application.In the accompanying drawings:
Fig. 1 is the stereoscan photograph (SEM) of sample prepared by the embodiment of the present invention 1, wherein (a) and (b) is un-sintered
Kelp before；(c) and (d) is the sample prepared after being sintered.
Fig. 2 is sample transmission electromicroscopic photograph (TEM) prepared by the embodiment of the present invention 1, wherein (a) shows that nanoparticle is equal
Even is distributed on porous carbon；(b) show nanoparticle by Multi-layer graphite carbon coating wherein.
Fig. 3 is sample X ray diffracting spectrum (XRD) prepared by the embodiment of the present invention 1.
Fig. 4 is sample N prepared by the embodiment of the present invention 12Adsorption-desorption curve (a) and pore-size distribution (b).
Fig. 5 is that the embodiment of the present invention 1 prepares catalytic performance test result figure of the sample in oxygen reduction reaction (ORR).
Fig. 6 is the influence experimental result picture of different sintering temperatures (a) or different load capacity (b) to electrocatalysis characteristic.
Fig. 7 is that the embodiment of the present invention 1 prepares stability (a) and methanol tolerance performance of the sample in oxygen reduction reaction (ORR)
(b) test result figure.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Below
Description only actually at least one exemplary embodiment be it is illustrative, never as to the present invention and its application or make
Any restrictions.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material as used in the following examples etc., is commercially available unless otherwise specified.
Embodiment 1
Step 1 washs kelp 3-5 times with 200ml deionized water.
Step 2, after the kelp washed is cut into the fritter of 1cm, 60-80 DEG C vacuum drying 6-12 hours.
Dry kelp 1g is put into 50ml and contains 0.10M-1.0MCo (NO by step 33)2Aqueous solution in, impregnate 6-12 it is small
When, until kelp fully absorbs solution.
Step 4, by the kelp impregnated with 200ml deionized water short rinse 3-5 times, then at 60-80 DEG C vacuum is dry
It is 6-12 hours dry.
Step 5, by the kelp handled well in nitrogen atmosphere 600-1000 DEG C calcining 2-3 hours；Heating rate is 5-10
DEG C/min；The derivative complex carbon material of kelp is made in natural cooling after having calcined.
4.0 milligrams of materials obtained above are dispersed in the mixed liquor of 960 μ L ethyl alcohol and 40 μ L naphthalene sweet smell, 60 points of ultrasound
Clock obtains carbon-supported transition-metal catalyst.The catalyst can be anti-with the redox of catalytic cathode in a fuel cell
It answers.
Technical problem of the present invention can be solved by the carbon-supported transition-metal catalyst that the above method is prepared,
Reach advantageous effects of the present invention, the present embodiment has been specifically chosen following preparation methods:
Firstly, being washed kelp 5 times with 200ml deionized water.It is 12 hours dry at 70 DEG C after being cut into the fritter of 1cm,
Dry kelp is put into 50ml and contains 1.0MCo (NO3)2Solution in, impregnate 12 hours, until kelp fully absorbs solution.It will leaching
The kelp steeped is dried in vacuo 12 hours with 200ml deionized water short rinse 3 times, then at 70 DEG C.Finally, by the sea of processing
Band is calcined 2 hours for 1000 DEG C in nitrogen atmosphere；Heating rate is 5 degrees/min, rear natural cooling, and it is compound that kelp derivative is made
Carbon material.
4.0 milligrams of materials obtained above are dispersed in ultrasound 60 minutes in the mixed liquor of 960 μ L ethyl alcohol and 40 μ L naphthalene sweet smell,
Carbon-supported transition-metal catalyst is obtained, Co/KCM-1000 is named as.
Embodiment 2
Firstly, being washed with deionized kelp 5 times.After being cut into the fritter of 1cm, in 80 DEG C of dry 8h, by dry kelp
It is put into 50ml and contains 0.5MCo (NO3)2Solution in, impregnate 12 hours, until kelp fully absorbs solution.The sea that will be impregnated
Band is used 200ml deionized water short rinse 3 times, then is dried in vacuo 8h at 80 DEG C.Finally, by the kelp of processing in nitrogen atmosphere
In 1000 DEG C calcine 2 hours；Heating rate is 5 degrees/min, rear natural cooling, and the derivative complex carbon material of kelp is made.
The derivative complex carbon material of 4.0 milligrams of kelps obtained above is dispersed in the mixing of 960 μ L ethyl alcohol and 40 μ L naphthalene sweet smell
Ultrasound 60 minutes, obtain carbon-supported transition-metal catalyst in liquid.
Embodiment 3
Firstly, being washed with deionized kelp 5 times.After being cut into the fritter of 1cm, in 60 DEG C of dry 12h, by dry kelp
It is put into containing 0.1M Co (NO3)2Solution in, impregnate 12 hours, until kelp fully absorbs solution.The kelp impregnated is used
200ml deionized water short rinse 3 times, then 8h is dried in vacuo at 60 DEG C.Finally, by the kelp of processing in nitrogen atmosphere
1000 DEG C are calcined 2 hours；Heating rate is 5 degrees/min, rear natural cooling, and the derivative complex carbon material of kelp is made.
4.0 milligrams of materials obtained above are dispersed in ultrasound 60 minutes in the mixed liquor of 960 μ L ethyl alcohol and 40 μ L naphthalene sweet smell,
Obtain carbon-supported transition-metal catalyst.
Embodiment 4
Firstly, being washed with deionized kelp 5 times.After being cut into the fritter of 1cm, in 60 DEG C of dry 12h, by dry kelp
It is put into containing 1.0M Co (NO3)2Solution in, impregnate 12 hours, until kelp fully absorbs solution.The kelp impregnated is used
200ml ionized water short rinse 3 times, then 8h is dried in vacuo at 60 DEG C.Finally, by the kelp of processing 650 in nitrogen atmosphere
DEG C calcining 2 hours；Heating rate is 5 degrees/min, rear natural cooling, and the derivative complex carbon material of kelp is made.
4.0 milligrams of materials obtained above are dispersed in ultrasound 60 minutes in the mixed liquor of 960 μ L ethyl alcohol and 40 μ L naphthalene sweet smell,
Obtain carbon-supported transition-metal catalyst.
Embodiment 5
Firstly, being washed with deionized kelp 5 times.After being cut into the fritter of 1cm, in 60 DEG C of dry 12h, by dry kelp
It is put into containing 1.0M Co (NO3)2Solution in, impregnate 12 hours, until kelp fully absorbs solution.The kelp impregnated is used
200ml ionized water short rinse 3 times, then 8h is dried in vacuo at 60 DEG C.Finally, by the kelp of processing 800 in nitrogen atmosphere
DEG C calcining 2 hours；Heating rate is 5 degrees/min, rear natural cooling, and the derivative complex carbon material of kelp is made.
4.0 milligrams of materials obtained above are dispersed in ultrasound 60 minutes in the mixed liquor of 960 μ L ethyl alcohol and 40 μ L naphthalene sweet smell,
Obtain carbon-supported transition-metal catalyst.
Comparative example 1
As control, 0.5M Co (NO will be contained in above-described embodiment 23)2Solution be substituted for the deionized water of same amount,
His condition is constant to obtain carbon material derived from kelp.
Carbon material derived from 4.0 milligrams of kelps obtained above is dispersed in 960 μ L ethyl alcohol and fragrant mixed of 40 μ L naphthalenes respectively
Ultrasound 60 minutes in liquid are closed, C catalyst is obtained, is named as KCM-1000.
Test case 1, constituent characterization test
Electronic Speculum, transmission electricity are scanned to the derivative complex carbon material of kelp made from unsintered kelp and embodiment 1
Mirror, X-ray diffraction and N2Adsorption-desorption test.
Scanning electron microscope (SEM) result is as shown in Figure 1, (a) and (b) has bright it can be seen that dry kelp structure is comparatively dense
Aobvious pleated structure (c) shows that sintered sample is apparent porous structure, (d) is further illustrated in the surface distribution of carbon
There is a large amount of nanoparticle.
Transmission electron microscope (TEM) result is as shown in Fig. 2, as can be seen that nanoparticle is uniformly distributed in porous carbon from (a)
On；From in (b) as can be seen that nanoparticle by Multi-layer graphite carbon coating wherein.
The XRD of Fig. 3 the result shows that Co nanoparticle presence, the derivative complex carbon material of kelp made from embodiment 1 wrapped
The essential element contained is carbon, oxygen, nitrogen, cobalt etc..
It is a kind of with special nucleocapsid by Fig. 1, Fig. 2 and Fig. 3 it is found that kelp produced by the present invention derives complex carbon material
The composite construction of the carbon coating cobalt nano-particle of structure, wherein the form of carbon be graphitized carbon, cobalt nano-particle partial size 5nm~
Between 20nm, cobalt nano-particle is located at the inside configuration that Multi-layer graphite carbon is coated.
In addition, Fig. 4 the result shows that, the specific surface area of the derivative complex carbon material of kelp made from embodiment 1 is 147m2g-1,
Characteristic aperture is 4nm.
Test case 2, the test of ORR catalytic capability
The carbon catalysis of carbon-supported transition-metal catalyst Co/KCM-1000, the preparation of comparative example 1 prepared by Example 1
Each 5 μ L of agent KCM-1000, drips respectively in glassy carbon electrode surface, is then dried at room temperature for.It is saturated respectively in oxygen at room temperature
Cyclic voltammetry is carried out in the 0.1M KOH solution of nitrogen saturation.Wherein, cyclic voltammetry is that there are three electrode systems in tool
What the CHI 700E electrochemical workstation of system carried out.Work is used as using vitreous carbon rotating disc electrode (RDE) (diameter 5mm, Pine)
Make electrode.It is respectively Pt and Ag/AgCl electrode to electrode and reference electrode.
In order to compare, 5 μ L commercialization Pt/C catalyst (20wt%Pt) are dripped in glass-carbon electrode table with same method
Face carries out identical test.
Test results are shown in figure 5, wherein (a) shows carbon-supported transition-metal catalyst Co/ prepared by embodiment 1
KCM-1000 is to O2With good ORR catalytic capability；(b) show KCM- made of the carbon material of blank prepared by comparative example 1
1000 catalyst, electrocatalysis characteristic is poor, and embodiment 1 is compounded with catalyst Co/KCM-1000 made of the material of transition metal
Shown carrying current is also higher than business Pt/C, further demonstrates its good ORR catalytic performance；(c) show with (d)
Electron transfer number of the material in ORR catalytic process is 4 (for desired quantity).
The influence test of test case 3, different sintering temperatures or different load capacity to electrocatalysis characteristic
This test case is to compare different sintering temperatures and different load capacity and (be embodied in the concentration of presoma Co salt
On) influence to electrocatalysis characteristic.Each 5 μ L drop of carbon-supported transition-metal catalyst that embodiment 1,2,3,4,5 obtains is existed
Then glassy carbon electrode surface is dried at room temperature for.It is rotated in the 0.1M KOH solution of oxygen saturation using vitreous carbon at room temperature
Disc electrode (RDE) (diameter 5mm, Pine) is used as working electrode.It is respectively Pt and Ag/AgCl electricity to electrode and reference electrode
Pole.Revolving speed is 1600rpm.
In order to compare, 5 μ L commercialization Pt/C catalyst (20wt%Pt) are dripped in glass-carbon electrode table with same method
Face carries out identical test.
Test results are shown in figure 6.The influence of sintering temperature: when sintering temperature be 1000 DEG C, gained sample Co/ST1000
That is the carbon-supported transition-metal catalyst of the preparation of embodiment 1, has preferable catalytic effect, in contrast, 650 DEG C and 800
DEG C (embodiment 4 prepare carbon-supported transition-metal catalyst be labeled as Co/ST650The carbon-supported mistake prepared with embodiment 5
Metallic catalyst is crossed labeled as Co/ST800) under the conditions of the catalyst for preparing, catalytic effect is poor, is mainly reflected in carrying current
Density is lower.The influence of predecessor concentration: when Co salt precursor bulk concentration is 0.5M (carbon-supported transition gold prepared by embodiment 2
Metal catalyst) or when 1.0M (embodiment 1 prepare carbon-supported transition-metal catalyst), the catalytic effect of gained sample compared with
It is good.
Test case 4, stability test and methanol tolerance performance test
The 5 μ L drop of carbon-supported transition-metal catalyst that Example 1 obtains is in glassy carbon electrode surface, then at room temperature
It is dry.Linear scan test is carried out in the 0.1M KOH solution of oxygen saturation at room temperature, linear scan test is such as to survey
Try what electrochemical workstation described in example 2 carried out, revolving speed 1600rpm is recorded as initial linear scan data.It is steady in order to carry out
Qualitative test has carried out 5000 cyclic voltammetries, carries out linear scan test again in 1600rpm later, is recorded as final
Linear scanning data is compared with starting.In order to carry out methanol tolerance performance test, we are in 150ml0.1M KOH solution
It joined 2ml methanol, carry out linear scan test later.
Test results are shown in figure 7, in (a), the Co/KCM-1000 first run test, represent embodiment 1 obtain it is carbon-supported
The initial linear sweep test result of transition-metal catalyst；After Co/KCM-1000 5000 times circulations, represents embodiment 1 and obtain
5000 times of carbon-supported transition-metal catalyst circulations after linear scan test result.(b) the result shows that, be added first
Before and after alcohol, the two lines sweep test curve of Co/KCM-1000 is essentially coincided, and represents the catalytic performance of the sample not by methanol
Influence, prove it with preferable methanol tolerance performance with this.
Claims (10)
1. a kind of material, which is characterized in that the material is made after being calcined by the kelp for impregnating cobalt-carrying solution.
2. material according to claim 1, which is characterized in that the material further includes following 1) -14) it is described at least
It is a kind of:
1) calcining is calcined including 600 DEG C or more；
2) calcining includes calcining 1 hour or more；
3) calcining, which is included in nitrogen atmosphere, calcines；
4) it is 5-10 DEG C/min that the calcining, which includes heating rate,；
5) kelp includes dry kelp；
6) described impregnate includes the dry kelp of soaking 1g in every 50ml cobalt-carrying solution；
7) described impregnate includes being dipped to until kelp fully absorbs cobalt-carrying solution；
8) soaking includes soaking 6-12 hours；
9) cobalt-carrying solution includes the (NO containing Co3)2Aqueous solution；
10) cobalt-carrying solution includes that concentration of cobalt ions is 0.10M-1.0M in solution；
It 11) further include washing, dry kelp before the soaking；
It 12) further include rinsing, dry kelp after the soaking；
It 13) further include natural cooling after the calcining；
14) material includes calcined product graphitized carbon and cobalt nanometer particle.
3. according to claim 1 and/or 2 any materials, which is characterized in that the material further includes following 1) -6) institute
At least one of state:
1) calcining includes 650 DEG C~1000 DEG C calcinings；
Specifically, 800 DEG C~1000 DEG C calcinings；Again specifically, 800 DEG C or 1000 DEG C calcinings；
2) calcining includes calcining 2-3 hours；
Specifically, calcining 2 hours；
3) it is 5 DEG C/min that the calcining, which includes heating rate,；
4) soaking includes soaking 12 hours；
5) cobalt-carrying solution includes that concentration of cobalt ions is 0.5M-1.0M in solution；
Specifically, being 0.5M or 1.0M；
6) when the material includes calcined product graphitized carbon and cobalt nanometer particle, the material further includes core-shell structure, institute
State graphitized carbon cladding cobalt nanometer particle；And/or the specific surface area of material is 147m2g-1, characteristic aperture 4nm；
Specifically, the partial size of the cobalt nanometer particle is between 5nm~20nm.
4. a kind of preparation method of material, which is characterized in that the described method includes: by after the kelp calcining for impregnating cobalt-carrying solution
Up to the material.
5. according to the method described in claim 4, it is characterized in that, the method also includes following 1) -13) it is described at least
It is a kind of:
1) calcining is calcined including 600 DEG C or more；
2) calcining includes calcining 1 hour or more；
3) calcining, which is included in nitrogen atmosphere, calcines；
4) it is 5-10 DEG C/min that the calcining, which includes heating rate,；
5) kelp includes dry kelp；
6) described impregnate includes the dry kelp of soaking 1g in every 50ml cobalt-carrying solution；
7) described impregnate includes being dipped to until kelp fully absorbs cobalt-carrying solution；
8) soaking includes soaking 6-12 hours；
9) cobalt-carrying solution includes the (NO containing Co3)2Aqueous solution；
10) cobalt-carrying solution includes that concentration of cobalt ions is 0.10M-1.0M in solution；
It 11) further include washing, dry kelp before the soaking；
It 12) further include rinsing, dry kelp after the soaking；
It 13) further include natural cooling after the calcining.
6. according to any method of claim 4 and/or 5, which is characterized in that the method also includes following 1) -5) institute
At least one of state:
1) calcining includes 650 DEG C~1000 DEG C calcinings；
Specifically, 800 DEG C~1000 DEG C calcinings；Again specifically, 800 DEG C or 1000 DEG C calcinings；
2) calcining includes calcining 2-3 hours；
Specifically, calcining 2 hours；
3) it is 5 DEG C/min that the calcining, which includes heating rate,；
4) soaking includes soaking 12 hours；
5) cobalt-carrying solution includes that concentration of cobalt ions is 0.5M-1.0M in solution；
Specifically, being 0.5M or 1.0M.
7. a kind of catalyst, which is characterized in that the catalyst include: by any material of claim 1,2 and/or 3 or
The material that claim 4,5 and/or 6 any the methods are directly prepared is dispersed in the mixed liquor of ethyl alcohol and naphthalene sweet smell, is surpassed
After sound to obtain the final product.
Specifically, the ultrasound includes ultrasound 60 minutes；The volume ratio of the ethyl alcohol and naphthalene sweet smell is 24:1.
8. a kind of preparation method of catalyst, which is characterized in that the described method includes: by any institute of claim 1,2 and/or 3
It states the material that material or claim 4,5 and/or 6 any the methods are directly prepared and is dispersed in fragrant mixed of ethyl alcohol and naphthalene
It closes in liquid, after ultrasound to obtain the final product.
Specifically, the ultrasound includes ultrasound 60 minutes；The volume ratio of the ethyl alcohol and naphthalene sweet smell is 24:1.
9. claim 1,2 and/or 3 any materials, claim 4,5 and/or 6 any the methods are directly prepared
Material, the application of catalyst that is directly prepared of catalyst or claim 8 the method described in claim 7.
Specifically, the application includes: the cathode material as fuel cell.
10. the application of claim 4,5 and/or 6 any the methods or claim 8 the method.
Specifically, the application includes, the application in fuel cell or its Related product is being prepared.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961130A (en) * | 2019-11-11 | 2020-04-07 | 中国地质大学（北京） | Non-noble metal Ni-C composite nano catalyst for efficient full water splitting and preparation method thereof |
| CN110961131A (en) * | 2019-11-12 | 2020-04-07 | 中国地质大学（北京） | Pt/C-N composite electro-catalytic material with efficient hydrogen evolution performance and preparation method thereof |
| CN111346642A (en) * | 2020-02-05 | 2020-06-30 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN112290025A (en) * | 2020-11-11 | 2021-01-29 | 瓮福（集团）有限责任公司 | Preparation method of electrode material based on carbonized kelp and lithium-sulfur battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| US20180254491A1 (en) * | 2017-03-06 | 2018-09-06 | Korea Institute Of Science And Technology | Method for preparing metal catalyst supported in porous carbon support using plant |
-
2018
- 2018-10-29 CN CN201811265043.7A patent/CN109301260A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445177A (en) * | 2014-12-16 | 2015-03-25 | 中国科学院宁波材料技术与工程研究所 | Preparation method of graphene, and graphene |
| US20180254491A1 (en) * | 2017-03-06 | 2018-09-06 | Korea Institute Of Science And Technology | Method for preparing metal catalyst supported in porous carbon support using plant |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110961130A (en) * | 2019-11-11 | 2020-04-07 | 中国地质大学（北京） | Non-noble metal Ni-C composite nano catalyst for efficient full water splitting and preparation method thereof |
| CN110961131A (en) * | 2019-11-12 | 2020-04-07 | 中国地质大学（北京） | Pt/C-N composite electro-catalytic material with efficient hydrogen evolution performance and preparation method thereof |
| CN111346642A (en) * | 2020-02-05 | 2020-06-30 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN111346642B (en) * | 2020-02-05 | 2023-02-28 | 临沂大学 | High-dispersion metal nanoparticle/biomass carbon composite electrode material and preparation method and application thereof |
| CN112290025A (en) * | 2020-11-11 | 2021-01-29 | 瓮福（集团）有限责任公司 | Preparation method of electrode material based on carbonized kelp and lithium-sulfur battery |
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