CN104624191A - CoO/C catalyst and preparation method thereof - Google Patents
CoO/C catalyst and preparation method thereof Download PDFInfo
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- CN104624191A CN104624191A CN201310564050.8A CN201310564050A CN104624191A CN 104624191 A CN104624191 A CN 104624191A CN 201310564050 A CN201310564050 A CN 201310564050A CN 104624191 A CN104624191 A CN 104624191A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a CoO/C catalyst, wherein loading of CoO in the catalyst is 0.01-99.99%, particle size of CoO in the catalyst is 3.5-50nm. A preparation method of the catalyst comprises the following steps: 1)preparation of nano particles: using ammoniacal liquor for hydrolyzing soluble cobalt salt, performing high temperature backflow on its mixing solution to obtain a colloidal solution or a black solid; 2)preparation of CoO/C: uniformly mixing the substance in the step 1) and powdered carbon in a solvent, removing the solvent and drying to obtain the black powder, performing temperature programming on the black powder, performing heat treatment under target temperature to obtain the CoO/C catalyst. The catalyst has the advantages of high oxygen reduction activity under alkaline condition, good stability, low cost of raw materials and preparation, simple preparation technology, and easy batch production, and is very suitable for being as an oxygen reduction catalyst of a metal/air fuel battery, an alkaline polymer dielectric membrane fuel cell under alkaline condition.
Description
Technical field
The present invention relates to a kind of alkaline oxygen reduction catalyst, relate to a kind of for the oxygen reduction catalyst under metal air fuel cell, alkaline polymer electrolyte membrane fuel cell and other alkali conditions specifically.
The invention still further relates to the preparation method of above-mentioned catalyst.
Background technology
Along with the exhaustion of petroleum resources and the demand of reduction greenhouse gas emission, development of new clean energy technology become study hotspot, and fuel cell and the first-selection that has the metal-air battery of the title of semi-fuel cell to become clean energy technology of future generation already because its energy conversion efficiency is high, pollution-free, easy to use.As everyone knows, oxygen reduction reaction (ORR) is as the cathode reaction of fuel cell and metal-air battery, and it is a dynamics slow process, even if on clean metal platinum surface, still have the overpotential of 300mV.At present, the highest active catalysis ORR eelctro-catalyst is still Pt base eelctro-catalyst, and its high price and limited resource reserve, it can not be applied on a large scale.Exploitation base metal ORR eelctro-catalyst seems particularly urgent to the commercialization realizing fuel cell and metal-air battery.In numerous base metal ORR catalyst, cobalt oxide (CoOx) shows suitable Activity and stabill, the Co that Dai et al. reports
3o
4the ORR activity of the carbon nano tube compound material that the composite of the Graphene adulterated with N and CoO and N adulterate in alkaline 1M NaOH is suitable with commodity Pt/C catalyst, and the catalysis ORR activity of CoO composite is more better than Co
3o
4.Therefore, controlled synthesis CoO nano particle be research CoO to the precondition of ORR electro catalytic mechanism and exploitation high activity based on the basis of CoO nano material ORR eelctro-catalyst, there is very high theory significance and using value.At present, the synthesis of the small size nanoscale CoO particle reported in document major part based on taking organic cobalt salt as precursor [Chem.Mater.1999,11,2702-2708/Chem.Mater.2010,22,4446 – 4454/], and adds PVP etc. as protective agent.The deficiency of this method is the expensive of organic cobalt salt, and protective agent is not easily removed simultaneously.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is to provide oxygen reduction electro-catalyst of a kind of high-performance be applied under metal air fuel cell, alkaline polymer electrolyte membrane fuel cell and other alkali conditions, size tunable and preparation method thereof.
For achieving the above object, the present invention adopts following concrete scheme to realize:
A kind of CoO/C catalyst, CoO loading is in the catalyst 0.01%-99%; The particle diameter of CoO is 2-50nm.
Described CoO loading is in the catalyst more excellent is 1%-40%.
Described CoO loading optimum is in the catalyst 1%-20%.
In described catalyst, the particle diameter of CoO is more excellent is 3-20nm.
In described catalyst, the particle diameter optimum of CoO is 3.5-8nm.
The preparation method of described CoO/C catalyst, comprises following preparation process:
(1) preparation of nano particle:
A. in solvent, add water-soluble cobalt salt and ammonia spirit and make it mix rear formation suspension;
B. the suspension that step (1) a obtains is placed in oil bath pan and is back to the mixture obtaining dark brown yellow CoOx colloidal solution or CoO black solid or said two devices; 1≤X≤4/3;
(2) preparation of CoO/C catalyst:
A. after adding carbon carrier in solvent, ultrasonic disperse is to forming homogeneous slurry;
B. in step (2) a gained slurries, add step (1) products therefrom, except desolventizing after mixing, be dried to afterwards and obtain black powder;
C. the black powder grinding obtained by step (2) b is placed in quartz or ceramic vessel, and under inertia and/or reducing gas atmosphere, temperature programming is to target temperature, and heat treatment under this target temperature, obtain target product CoO/C catalyst.
In the preparation method of described CoO/C catalyst:
In step (1) a, described cobalt salt is one or more in cobalt nitrate, cobaltous sulfate, cobalt acetate, cobalt chloride; Described cobalt salt is 1:4-1:40 with the ratio of the amount of substance of ammoniacal liquor; Described solvent is ethanol, water or the mixture of the two; The concentration of described cobalt salt in solvent is 0.001-1M;
In step (1) b, the reflux temperature of described oil bath pan is 70-160 DEG C, and described return time is 3-8h;
In step (2) a, described carbon carrier is one or more in XC-72, BP, MWCNT, Graphene;
In step (2) b, described baking temperature is 80-120 DEG C;
In step (2) c, described inertia and/or reducing gas atmosphere or be N
2, Ar, H
2in one or more gaseous mixture, or be NH
3, or be NH
3with N
2, one or both gaseous mixture in Ar; Described target temperature is 250-900 DEG C; Described target temperature is more excellent is 350-800 DEG C; Described step target temperature optimum is 400-650 DEG C; Described programmed rate is 1-10 DEG C/min; Heat treatment time is 2-6h.
Under CoO/C catalyst of the present invention has alkali condition, oxygen reduction activity is high, good stability, abundant raw material source and with low cost, and preparation process is simple, is conducive to the advantages such as the large-scale production of product.
Accompanying drawing explanation
Fig. 1 is the XRD spectra (embodiment 1,2,3) of the CoO/C catalyst of the identical CoO carrying capacity adopting variable concentrations acetic acid cobalt salt precursor to prepare.
The TEM photo (left side) of CoO/C catalyst prepared by Fig. 2 embodiment 1 and domain size distribution statistical chart (right side).
The TEM photo (left side) of CoO/C catalyst prepared by Fig. 3 embodiment 2 and domain size distribution statistical chart (right side).
The TEM photo (left side) of CoO/C catalyst prepared by Fig. 4 embodiment 3 and domain size distribution statistical chart (right side).
Fig. 5 is that the ORR curve of CoO/C catalyst under 0.1M NaOH condition of the identical CoO carrying capacity adopting variable concentrations acetic acid cobalt salt precursor to prepare compares.
Fig. 6 is the XRD spectra of the CoO/C catalyst of the identical CoO carrying capacity adopting the different heat treatment time to prepare.
The stability of the catalyst of Fig. 7 prepared by embodiment 2 under 0.1M NaOH condition and the contrast of commercial catalyst.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is explained in detail.Certain the present invention is not limited in these specific embodiments.
Embodiment 1:
First, by 0.25g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 1.25mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 1mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 5mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 5.88%CoO/C catalyst.From XRD spectra also through calculating, in catalyst, the particle diameter of CoO is 5.14nm.
Embodiment 2:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 1mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 5mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 5.88%CoO/C catalyst.From XRD spectra also through calculating, in catalyst, the particle diameter of CoO is 3.95nm.
Embodiment 3:
First, by 1.25g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 6.25mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 1mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 5mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 5.88%CoO/C catalyst.From XRD spectra also through calculating, in catalyst, the particle diameter of CoO is 6.84nm.
As can be seen from Figure 1, in the 5.88%CoO/C catalyst prepared by the inventive method, cobalt oxide is CoO thing phase.
As can be seen from Figure 2, in the 5.88%CoO/C catalyst prepared by embodiment 1, CoO is evenly distributed, and average grain diameter is 4.9nm.
As can be seen from Figure 3, in the 5.88%CoO/C catalyst prepared by embodiment 2, CoO is evenly distributed, and average grain diameter is 3.5nm.
As can be seen from Figure 4, in the 5.88%CoO/C catalyst prepared by embodiment 3, CoO is evenly distributed, and average grain diameter is 6.5nm.
As can be seen from Figure 5, the 5%CoO/C catalyst prepared by embodiment 1,2,3 is followed successively by as embodiment 2> embodiment 1> embodiment 3 from high to low to the activity of ORR
Embodiment 4:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 1mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 5mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 0.5h namely obtain target product 5.88%CoO/C catalyst.
Prepared by known from Fig. 6 XRD spectra, 5.88%CoO/C is single CoO thing phase, and the particle diameter that process calculates CoO in catalyst is 3.45nm.
Embodiment 5:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 1mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 5mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 4h namely obtain target product 5.88%CoO/C catalyst.
Prepared by known from Fig. 6 XRD spectra, 5.88%CoO/C is single CoO thing phase, and the particle diameter that process calculates CoO in catalyst is 4.75nm.
Embodiment 6:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 0.2mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 1mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 1.23%CoO/C catalyst.
Embodiment 7:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 2mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 10mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 11.1%CoO/C catalyst.
Embodiment 8:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 4mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 20mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 20%CoO/C catalyst.
Embodiment 9:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 8mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 40mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 33.3%CoO/C catalyst.
Embodiment 10:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL absolute ethyl alcohol, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain CoO
xcolloid.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The CoO that 11mL obtains is added in these slurries
xcolloidal solution (metal Co quality is 55mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 500 DEG C, and at this temperature process 2h namely obtain target product 40.7%CoO/C catalyst.
Embodiment 11:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL deionized water, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain Co
3o
4black suspension.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The Co that 1mL obtains is added in these slurries
3o
4black suspension (metal Co quality is 5mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 800 DEG C, and at this temperature process 2h namely obtain target product 5.88%CoO/C catalyst.From XRD spectra as calculated CoO nano particle diameter be 20nm.
Embodiment 12:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL deionized water, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain Co
3o
4black suspension.
Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The Co that 2mL obtains is added in these slurries
3o
4black suspension (metal Co quality is 10mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 800 DEG C, and at this temperature process 2h namely obtain target product 11.1%CoO/C catalyst.From XRD spectra as calculated CoO nano particle diameter be 26nm.
Embodiment 13:
First, by 0.5g Co (OAc)
24H
2o is dissolved in 25mL deionized water, adds 2.5mL25w.t.% ammoniacal liquor, mixture is placed in air and stirs 15min; Then transfer them in the oil bath pan of 100 DEG C and carry out adding hot reflux, lower the temperature after 3.5h, be naturally chilled to room temperature, obtain Co
3o
4black suspension.Take 80mg Vulcan XC-72 carbon black, add 25mL absolute ethyl alcohol, ultrasonic disperse is even; The Co that 4mL obtains is added in these slurries
3o
4black suspension (metal Co quality is 20mg), room temperature lower magnetic force stirs 6h.Then mixture is removed desolventizing by Rotary Evaporators, be placed in the dry 8h of 80 DEG C of air-ovens, obtain CoO
x/ C.By obtained black powder CoO
x/ C grinds, weighs and be placed in quartz boat, is then transferred to tube furnace, and at N
2with 5 DEG C of min under atmosphere
-1rate program be warming up to 800 DEG C, and at this temperature process 2h namely obtain target product 20%CoO/C catalyst.From XRD spectra as calculated CoO nano particle diameter be 40nm.
ORR Performance comparision under the particle diameter of CoO/C catalyst obtained under table different condition and 0.1M NaOH condition
| Embodiment | CoO carrying capacity/% | CoO particle diameter/nm | Half wave potential/mV |
| Embodiment 1 | 5.88 | 4.9 | -0.17 |
| Embodiment 2 | 5.88 | 3.5 | -0.15 |
| Embodiment 3 | 5.88 | 6.5 | -0.19 |
| Embodiment 4 | 5.88 | 3.4 | -0.18 |
| Embodiment 5 | 5.88 | 4.8 | -0.16 |
| Embodiment 6 | 1.23 | 3 | -0.17 |
| Embodiment 7 | 11.1 | 4 | -0.17 |
| Embodiment 8 | 20 | 5 | -0.18 |
| Embodiment 9 | 33.3 | 6 | -0.19 |
| Embodiment 10 | 40.7 | 8 | -0.22 |
| Embodiment 11 | 5.88 | 20 | -0.25 |
| Embodiment 12 | 11.1 | 26 | -0.28 |
| Embodiment 13 | 20 | 40 | -0.30 |
Catalyst of the present invention has that oxygen reduction activity under alkali condition is high, good stability, raw material and preparation cost cheap, preparation technology is simple, be easy to the advantages such as batch production, be suitable for very much as the oxygen reduction catalyst under the alkali conditions such as metal/air fuel cell, alkaline polymer electrolyte membrane fuel cell.
Claims (10)
1. a CoO/C catalyst, is characterized in that: CoO quality loading is in the catalyst 0.01%-99%, and surplus is C carrier; In catalyst, the particle diameter of CoO is 3-50nm.
2. CoO/C catalyst as claimed in claim 1, is characterized in that: described CoO quality loading is in the catalyst more excellent is 1%-40%.
3. CoO/C catalyst as claimed in claim 1, is characterized in that: described CoO quality loading optimum is in the catalyst 5%-20%.
4. CoO/C catalyst as described in claim 1,2 or 3, is characterized in that: in described catalyst, the particle diameter of CoO is more excellent is 3.5-20nm.
5. CoO/C catalyst as described in claim 1,2 or 3, is characterized in that: in described catalyst, the particle diameter optimum of CoO is 3.5-8nm.
6. a preparation method for the arbitrary described CoO/C catalyst of claim 1-5, is characterized in that: comprise following preparation process:
(1) preparation of nano particle:
A. in solvent, add water-soluble cobalt salt and ammonia spirit and make it mix rear formation suspension;
B. be back at suspension 70-160 DEG C that step (1) a is obtained and obtain dark brown yellow CoO
xcolloidal solution or Co
3o
4the mixture of black solid or said two devices; 1≤X≤4/3;
(2) preparation of CoO/C catalyst:
A. after adding carbon carrier in solvent, ultrasonic disperse is to forming homogeneous slurry;
B. in step (2) a gained slurries, add step (1) b products therefrom, except desolventizing after mixing, be dried to afterwards and obtain black powder;
C. the black powder grinding obtained by step (2) b is placed in quartz or ceramic vessel, and under inert atmosphere and/or reducing gas atmosphere, temperature programming is to target temperature, and is heat-treated under this target temperature and obtains target product CoO/C catalyst.
7. the preparation method of CoO/C catalyst as claimed in claim 6, is characterized in that:
Described cobalt salt is one or more in cobalt nitrate, cobaltous sulfate, cobalt acetate, cobalt chloride; Described cobalt salt is 1:4-1:40 with the ratio of the amount of substance of ammoniacal liquor;
Described carbon carrier is one or more in XC-72, BP, MWCNT, Graphene;
Described inertia and/or reducing gas atmosphere are N
2, Ar, H
2in one or more gaseous mixture, or be NH
3, or be NH
3with N
2, one or both gaseous mixture in Ar;
Described target temperature is 250-900 DEG C.
8. the preparation method of CoO/C catalyst as claimed in claim 7, is characterized in that: described target temperature is more excellent is 350-800 DEG C.
9. the preparation method of CoO/C catalyst as claimed in claim 8, is characterized in that: described target temperature optimum is 400-650 DEG C.
10. the preparation method of CoO/C catalyst as claimed in claim 6, is characterized in that:
In described step (1) a, solvent is ethanol, water or the mixture of the two, and the concentration of cobalt salt in solvent is 0.001-1M;
In described step (1) b, the reflux temperature of oil bath pan is 70-160 DEG C, and return time is 3-8h;
In described step (2) b, baking temperature is 80-120 DEG C; Described step (2) c Program heating rate is 1-10 DEG C/min, and heat treatment time is 2-6h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105655601A (en) * | 2016-03-28 | 2016-06-08 | 北方民族大学 | Preparation method and application of anode catalyst of direct borohydride fuel cell |
| CN106784709A (en) * | 2016-12-28 | 2017-05-31 | 山东理工大学 | A kind of preparation method of lithium ion battery negative material-cobalt-based composite |
| RU2723558C1 (en) * | 2019-12-20 | 2020-06-16 | федеральное государственное автономное образовательное учреждение высшего образования «Южный федеральный университет» | Method of producing nanostructured cobalt oxide on carbon support |
| CN115000432A (en) * | 2022-06-06 | 2022-09-02 | 广东工业大学 | Cobalt oxide-loofah sponge derived nitrogen-doped carbon composite material and preparation method and application thereof |
| CN115000432B (en) * | 2022-06-06 | 2023-09-08 | 广东工业大学 | Cobalt oxide-luffa derivative nitrogen-doped carbon composite material and preparation method and application thereof |
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