CN104162428A - Method for preparing support-type cobalt oxide catalyst - Google Patents
Method for preparing support-type cobalt oxide catalyst Download PDFInfo
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- CN104162428A CN104162428A CN201410330311.4A CN201410330311A CN104162428A CN 104162428 A CN104162428 A CN 104162428A CN 201410330311 A CN201410330311 A CN 201410330311A CN 104162428 A CN104162428 A CN 104162428A
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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 method for preparing a catalyst, which comprises the following steps: adding cobaltous chloride, a chelating agent and a carbon material in a solvent, reacting cobalt ion (CO<3+>) in cobaltous chloride and the chelating agent to form a cobalt complex attached on the carbon material to prepare the mixed liquor, drying the mixed liquor to obtain the dried product; and performing microwave treatment on the dried product to form the support-type cobalt oxide catalyst, wherein the support-type cobalt oxide catalyst contains a carrier and cobalt oxide particles supported on the carrier.
Description
Technical field
The present invention is about a kind of manufacture method of catalyst, and especially in regard to a kind of manufacture method of support type cobalt/cobalt oxide catalyst.
Background technology
Fuel cell possesses low dusty gas discharge, low noise and the advantage such as renewable, thereby be regarded as a environmental protection, cleaning and free of contamination generating equipment, and little by little in the purposes such as business, house and traffic, substitute as traditional petrochemical industry generating equipments such as diesel motor or gasoline engines.
The operation principle of fuel cell is as follows: after (1) hydrogen enters in battery, in the anode generation oxidation reaction of battery, and produce hydrogen ion (H
+) and discharge electronics, this process is called " anode half-reaction "; (2) electrolyte or PEM that the hydrogen ion producing sees through battery are the negative electrode that medium is sent to battery, and the electronics discharging sees through external circuit and is transported to negative electrode, carrys out generation current; (3) hydrogen ion transmitting and electronics and airborne oxygen, after negative electrode collects, in negative electrode generation reduction reaction, and produce water, and this process is called " negative electrode half-reaction ".Generally speaking, anode half-reaction and the reaction rate of negative electrode half-reaction under natural conditions are very slow, and can configure catalyst (also referred to as " catalyst ") on male or female, improve reaction rate, thereby promote the electrical property efficiency of battery.
At first, precious metal (as: platinum) and related compound thereof, alloy are used the catalyst into fuel cell widely.Though this catalyst can bring fuel cell gratifying electrical property efficiency, its content rareness and market value are not striking, and then the manufacturing cost of related lifting fuel cell, and hinder the but global development of fuel cell.In recent years, researcher pays close attention to the research of non-precious metal and related compound thereof, alloy one after another, expects that they can be as the catalyst of fuel cell.For instance, in the patent publication No. WO2004/106591 of A.Gulla Deng Ren World Intellectual Property Organization (WIPO), report a kind of oxygen reduction (oxygen reduction) and use catalyst.This catalyst is for being carried on electrical conductivity Carbon black and with Ru
xco
ys (x: y=0.2: 1 to 5: the 1) sulfide that general formula represents, its manufacture process is: electrical conductivity Carbon black is infiltrated in the matrix salting liquid of ruthenium and cobalt; Carbon black after dry infiltration; And processing is dried the product obtaining under hydrogen sulfide atmosphere.In addition for instance, Chen Yingjie Deng Renyu Republic of China patent of invention publication number 201223634 discloses a kind of alloy catalyst.This catalyst is by the palladium of 50 atom % to 98 atom %, the cobalt of 2 atom % to 30 atom % and 0.01 atom % form to the molybdenum that is less than 5 atom %, and its manufacture process is: carbon carrier is scattered in ethylene glycol, forms carbon carrier dispersion liquid; Palladium salt, cobalt salt and molybdenum saline solution are added in carbon carrier dispersion liquid, form glycol water; The pH value of adjusting glycol water, makes palladium salt, cobalt salt and molybdenum salt reduce and be adsorbed onto on carbon carrier, forms alloy catalyst; And under reducing atmosphere heat treatable alloy catalyst.
In summary, though metallic cobalt and related compound thereof, alloy as the catalyst several years of fuel cell, the manufacture process of this type of catalyst is too tediously long, is probably unfavorable for the extensive manufacture of fuel cell.Moreover the particle diameter of this class catalyst is generally uneven, makes fuel cell cannot bring into play the electrical property efficiency of optimization, more cannot reduce the manufacturing cost of fuel cell.
Summary of the invention
The object of the invention is to propose a kind of manufacture method of catalyst of novelty.And this method contains following steps: add cobalt chloride, chelating agent and carbonaceous material (carbonaceous material) to solvent, make the cobalt ions (Co in cobalt chloride
3+) react with chelating agent to form and be adsorbed in the cobalt complex on carbonaceous material, to make mixed liquor; Dry mixed liquid, to obtain desciccate; And microwave treatment desciccate, to form support type cobalt/cobalt oxide catalyst, and support type cobalt/cobalt oxide catalyst contains carrier and be carried on the cobalt/cobalt oxide particle of carrier.
According to the present invention, this method easily operates and quite saves time, thereby can facilitate and promptly obtain support type cobalt/cobalt oxide catalyst.In addition, cobalt/cobalt oxide particle in support type cobalt/cobalt oxide catalyst has the particle diameter of homogeneity, so when support type cobalt/cobalt oxide catalyst is during as the catalyst of fuel cell, not only can allow the electrical property efficiency of fuel cell performance optimization, still can reduce the manufacturing cost of overall fuel cell.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet, and the manufacture method of the catalyst of embodiment of the present invention is described.
Fig. 2 is transmission electron microscope (transmission electron microscope, TEM) photo figure, shows the outward appearance of the catalyst that preparation example 1 obtains.
Fig. 3 is transmission electron microscope photo figure, shows the outward appearance of the catalyst that preparation example 2 obtains.
Fig. 4 is transmission electron microscope photo figure, shows the outward appearance of the catalyst that preparation example 3 obtains.
Fig. 5 is transmission electron microscope photo figure, shows the outward appearance of the catalyst that preparation example 4 obtains.
Fig. 6 is transmission electron microscope photo figure, shows the outward appearance of the catalyst that preparation example 5 obtains.
Fig. 7 is transmission electron microscope photo figure, shows the outward appearance of the catalyst that preparation example 6 obtains.
Fig. 8 is X-ray diffraction analysis instrument result figure, and the composition of the catalyst that preparation example 1 to 5 obtains is described.
Fig. 9 is cyclic voltammetry result figure, and the electrochemical properties of the catalyst that preparation example 1 to 5 obtains is described.
Figure 10 is linear sweep voltammetry result figure, and the electrochemical properties of the catalyst that preparation example 1 to 5 obtains is described.
Figure 11 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 1 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm.
Figure 12 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 2 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm.
Figure 13 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 3 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm.
Figure 14 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 4 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm.
Figure 15 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 5 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm.
Figure 16 is cyclic voltammetry result figure, and the electrochemical properties of the catalyst that preparation example 6 to 10 obtains is described.
Figure 17 is linear sweep voltammetry result figure, and the electrochemical properties of the catalyst that preparation example 6 to 10 obtains is described.
Figure 18 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 6 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm, (5): 2,500rpm.
Figure 19 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 7 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm, (5): 2,500rpm.
Figure 20 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 8 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm, (5): 2,500rpm.
Figure 21 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 9 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm, (5): 2,500rpm.
Figure 22 is the linear sweep voltammetry result figure of collocation rotating disk electrode (r.d.e), and catalyst that preparation example 10 the obtains electrochemical properties under different rotating speeds is described; (1): 100rpm wherein, (2): 400rpm, (3): 900rpm, (4): 1,600rpm, (5): 2,500rpm.
The specific embodiment
For above-mentioned and/or other objects of the present invention, effect, feature more can be become apparent, below enumerate especially preferred embodiment, elaborate.
Refer to Fig. 1, in embodiments of the present invention, disclose a kind of manufacture method of catalyst, its detailed process is as following:
First, as shown in step S1, add cobalt chloride, chelating agent and carbonaceous material to solvent, make cobalt ions in cobalt chloride react formation with chelating agent and be adsorbed in the cobalt complex on carbonaceous material, and obtain mixed liquor.And, when carrying out step S1, in order to allow cobalt ions and chelating agent react rapidly formation cobalt complex, can under stirring solvent, limit add cobalt chloride, chelating agent and carbonaceous material to solvent.
" chelating agent " used herein second word, according to the technical field of the invention personnel general knowledge, define, refer to and there is two or above lone electron pair (hereinafter, also referred to as " ligand number "), and by the molecule of lone electron pair and central atom or ion (as: cobalt ions of present embodiment) formation coordinate bond.And, the example of chelating agent, can for but be not limited to ethylenediamine (ethylenediamine, referred to as " en "), 2, 2 '-bipyridyl (2, 2 '-bipyridine, referred to as " bpy "), Phen (phenanthroline, referred to as " phe "), diethylenetriamine (diethylenetriamine, referred to as " DETA "), porphyrin (porphyrin, referred to as " pp "), tricarboxylic ylmethyl ethylenediamine (tris-carboxymethyl ethylene diamine, referred to as " TED "), or ethylenediamine tetra-acetic acid (ethylenediaminetetraacetic acid, referred to as " EDTA ").
In addition, the example of carbonaceous material, can for but be not limited to carbon black.The example of solvent, can for but be not limited to ethanol, water or ethanol water.
Should be noted that, in the present embodiment, cobalt complex meets with following formula: [Co (R)
m(H
2o)
n]
3+, the R in formula represents chelating agent, m represents chelating agent with respect to the molal quantity ratio of cobalt ions and is H for being more than or equal to 1, n
2o is with respect to the molal quantity ratio of cobalt ions and for being more than or equal to 0, (ligand number of chelating agent) * m+n=6.From above formula, the ligand number of chelating agent can be 2,3,4,5 or 6.Ligand number is for example ethylenediamine, 2 of 2 chelating agent (claiming again " bidentate ligand "), 2 '-bipyridyl or Phen, and while adopting ethylenediamine to be chelating agent, cobalt complex can be expressed as [Co (en)
1(H
2o)
4]
3+, [Co (en)
2(H
2o)
2]
3+, [Co (en)
3]
3+, or these combinations.Ligand number is for example diethylenetriamine of 3 chelating agent (claiming again " tridentate ligand "), and while adopting diethylenetriamine to be chelating agent, cobalt complex can be expressed as [Co (DETA)
1(H
2o)
3]
3+, [Co (DETA)
2]
3+, or these combinations.Ligand number is for example porphyrin of 4 chelating agent (claim again " tetradentate ligands), and while adopting porphyrin to be chelating agent, cobalt complex can be expressed as [Co (pp)
1(H
2o)
2]
3+.Ligand number is for example tricarboxylic ylmethyl ethylenediamine of 5 chelating agent (claiming again " five tooth parts "), and while adopting tricarboxylic ylmethyl ethylenediamine to be chelating agent, cobalt complex can be expressed as [Co (TED)
1(H
2o)
1]
3+.Ligand number is for example ethylenediamine tetra-acetic acid of 6 chelating agent (claiming again " sexadentate ligand "), and while adopting ethylenediamine tetra-acetic acid to be chelating agent, cobalt complex can be expressed as [Co (EDTA)
1]
3+.
Secondly, as shown in step S2, ultrasonic wave is uniformly mixed liquid, and cobalt complex is uniformly distributed in mixed liquor.The visual demand of step S2 ground selectively carries out, and its time is unrestricted in principle, as long as can reach the object of this step.In present embodiment, the time is about 1 to 24 hour.
Then, as shown in step S3, dry mixed liquid, and obtain desciccate.When carrying out step S3, can bestow dehydration means in mixed liquor, and obtain desciccate.In present embodiment, dehydration means are carried out under vacuum environment.
Finally, as shown in step S4, microwave treatment desciccate, with the type cobalt/cobalt oxide catalyst that is supported, support type cobalt/cobalt oxide catalyst contains carrier and is carried on the cobalt/cobalt oxide particle of carrier.In principle, time and the microwave output power of step S4 are unrestricted, as long as can realize the object of this step.And in the present embodiment, the time is about 3 to 30 minutes, power output is about 100 to 3,000W.
In addition, in the present embodiment, cobalt/cobalt oxide particle is cobalt black (cobalt (II) oxide, CoO), cobalt sesquioxide (cobalt (III) oxide, Co
2o
3), cobaltosic oxide (cobalt (II, III) oxide, Co
3o
4) or these constitute.
The inventor observes a phenomenon to a miracle, and wherein the ligand number of chelating agent is 2 o'clock, and carrier is CNT; And the ligand number of chelating agent is 3,4,5 or 6 o'clock, carrier is above-mentioned carbonaceous material.In other words, the ligand number of chelating agent is 2 o'clock, and carbonaceous material can be transformed into CNT after step S4; And the ligand number of chelating agent is 3,4,5 or 6 o'clock, carbonaceous material is still maintained carbonaceous material after step S4.
Hereby with following embodiment, further illustrate embodiments of the present invention:
Preparation example 1
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the CoCL2 6H2O of 0.22mmol and the ethylenediamine of 0.22mmol to the aqueous solution, allows cobalt ions and reacting ethylenediamine form and is expressed as [Co (en)
1(H
2o)
4]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 2% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
As shown in Figure 2, arrow indication person is CNT, and the circle frame person of enclosing is cobalt/cobalt oxide particle, and particle is to be attached on carbon pipe, and its particle diameter is about 2 to 15nm.
Preparation example 2
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the CoCL2 6H2O of 0.22mmol and the diethylenetriamine of 0.22mmol to the aqueous solution, allows cobalt ions and diethylenetriamine reaction form and is expressed as [Co (DETA)
1(H
2o)
3]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 2% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
As shown in Figure 3, arrow indication person is carbon black, and the circle frame person of enclosing is cobalt/cobalt oxide particle, and particle is to be attached on carbon black, and its particle diameter is about 4 to 6nm.
Preparation example 3
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the CoCL2 6H2O of 0.22mmol and the porphyrin of 0.22mmol to the aqueous solution, allows cobalt ions and porphyrin reaction form and is expressed as [Co (pP)
1(H
2o)
2]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 2% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
As shown in Figure 4, arrow indication person is carbon black, and the circle frame person of enclosing is cobalt/cobalt oxide particle, and particle is to be attached on carbon black, and its particle diameter is about 2 to 5nm.
Preparation example 4
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the CoCL2 6H2O of 0.22mmol and the tricarboxylic ylmethyl ethylenediamine of 0.22mmol to the aqueous solution, allows cobalt ions and tricarboxylic ylmethyl reacting ethylenediamine form and is expressed as [Co (TED)
1(H
2o)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 2% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
As shown in Figure 5, arrow indication person is carbon black, and the circle frame person of enclosing is cobalt/cobalt oxide particle, and particle is to be attached on carbon black, and its particle diameter is about 5 to 10nm.
Preparation example 5
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the CoCL2 6H2O of 0.22mmol and the ethylenediamine tetra-acetic acid of 0.22mmol to the aqueous solution, allows cobalt ions and ethylenediamine tetra-acetic acid reaction form and is expressed as [Co (EDTA)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 2% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
As shown in Figure 6, arrow indication person is carbon black, and the circle frame person of enclosing is cobalt/cobalt oxide particle, and particle is to be attached on carbon black, and its particle diameter is about 20 to 40nm.
Preparation example 6
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the diethylenetriamine of the CoCL2 6H2O of 0.22mmol, the ethylenediamine of 0.22mmol and 0.22mmol to the aqueous solution, allows cobalt ions and ethylenediamine, diethylenetriamine reaction form and to be expressed as [Co (en)
1(DETA)
1(H
2o)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 2% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
As shown in Figure 7, arrow indication person is carbon black, and the circle frame person of enclosing is cobalt/cobalt oxide particle, and particle is to be attached on carbon black, and its particle diameter is about 4 to 6nm.
Preparation example 7
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the diethylenetriamine of the CoCL2 6H2O of 0.55mmol, the ethylenediamine of 0.55mmol and 0.55mmol to the aqueous solution, allows cobalt ions and ethylenediamine, diethylenetriamine reaction form and to be expressed as [Co (en)
1(DETA)
1(H
2o)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 5% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
According to the transmission electron microscope photo figure not showing, the catalyst of this preparation example has carbon black and cobalt/cobalt oxide particle, and particle is be attached on carbon black and have the particle diameter that is about 4 to 6nm.
Preparation example 8
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the diethylenetriamine of the CoCL2 6H2O of 1.1mmol, the ethylenediamine of 1.1mmol and 1.1mmol to the aqueous solution, allows cobalt ions and ethylenediamine, diethylenetriamine reaction form and to be expressed as [Co (en)
1(DETA)
1(H
2o)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 10% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
According to the transmission electron microscope photo figure not showing, the catalyst of this preparation example has carbon black and cobalt/cobalt oxide particle, and particle is be attached on carbon black and have the particle diameter that is about 4 to 6nm.
Preparation example 9
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the diethylenetriamine of the CoCL2 6H2O of 1.65mmol, the ethylenediamine of 1.65mmol and 1.65mmol to the aqueous solution, allows cobalt ions and ethylenediamine, diethylenetriamine reaction form and to be expressed as [Co (en)
1(DETA)
1(H
2o)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 15% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
According to the transmission electron microscope photo figure not showing, the catalyst of this preparation example has carbon black and cobalt/cobalt oxide particle, and particle is be attached on carbon black and have the particle diameter that is about 4 to 6nm.
Preparation example 10
First, when ethanol water (volume ratio of ethanol, water is 1: 1) is stirred on limit, limit adds the diethylenetriamine of the CoCL2 6H2O of 2.2mmol, the ethylenediamine of 2.2mmol and 2.2mmol to the aqueous solution, allows cobalt ions and ethylenediamine, diethylenetriamine reaction form and to be expressed as [Co (en)
1(DETA)
1(H
2o)
1]
3+cobalt complex.Add the Vulcan XC-72 carbon black of 450mg to the aqueous solution, allow carbon black adsorption of cobalt complex compound, and the cobalt ions that is adsorbed in carbon black is about 20% with respect to the weight ratio of carbon black.Then, the mixed liquor that ultrasonic wave processing obtains 24 hours, allows the cobalt complex in mixed liquor be uniformly distributed in wherein.Mixed liquor is placed in dewaterer, and utilizes dewaterer to dewater to mixed liquor under vacuum environment, allow the aqueous solution in mixed liquor remove and to obtain desciccate.Finally, utilize power output 2, the microwave treatment desciccate of 500W 10 minutes, and obtain catalyst.
According to the transmission electron microscope photo figure not showing, the catalyst of this preparation example has carbon black and a cobalt/cobalt oxide particle, and particle is be attached on carbon black and have the particle diameter that is about 4 to 6nm.
Analyze example 1
This analysis is to utilize X-ray diffraction analysis instrument (X-ray diffractometer, XRD) to confirm that the cobalt/cobalt oxide particle of aforementioned catalyst forms.During analysis, use Cu Ka to irradiate catalyst, and the collection of illustrative plates obtaining with 2 degrees/min of records of stride speed within the scope of in 2 θ=10 to 70 degree.
Refer to Fig. 8, with (the Joint Committee on Powder Diffraction Standards of JCPDS, JCPDS) after the contrast of numbering 71-1778 card, the cobalt/cobalt oxide particle that can estimate the catalyst of preparation example 2 contains cobalt black.In addition, after contrasting with JCPDS numbering 42-1467 card, the cobalt/cobalt oxide particle that can estimate the catalyst of preparation example 1 contains cobalt sesquioxide.Again, after contrasting with JCPDS numbering 02-0770 card, the cobalt/cobalt oxide particle that can estimate the catalyst of preparation example 3,4 and 5 contains cobaltosic oxide.
Analyze example 2
This analysis is to utilize cyclic voltammetry (cyclic voltammogram) to assess the electrochemical properties of aforementioned catalyst.Carry out before this method, the Nafion solution of the ethanol of the catalyst of 20mg, 120 μ l and 20 μ l (purchased from E.I.Du Pont Company, weight concentration is 5%) is mixed, then the mixed liquor obtaining with ultrasonic oscillation 30 minutes; Then, get the mixed liquor of 25 μ l, and coat area and be about the glassy carbon electrode that 0.066cm2 and thickness are 5mm; Finally, the glassy carbon electrode after drying coated, allows catalyst be fixed on glassy carbon electrode.During analysis, employing glassy carbon electrode is working electrode, and platinum line is auxiliary electrode, and silver/silver chlorate is reference electrode.And this method is to carry out in the sulfuric acid solution (molal volume concentration is 0.5M) of the 80ml under being full of oxygen atmosphere.
Refer to Fig. 9, preparation example 3,4 and 5 catalyst have obvious reduction wave peak current (cathodic current peak, ipc), and wherein the reduction wave peak current of the catalyst of preparation example 3 is the most remarkable.Hence one can see that, and in these five catalyst, the catalyst of preparation example 3 has best reduction reaction catalytic activity.
Please separately consult Figure 16, the catalyst of preparation example 6 to 10 all has obvious reduction wave peak current, and wherein the reduction wave peak current of the catalyst of preparation example 8 is the most obvious.Hence one can see that, and in these five catalyst, the catalyst of preparation example 8 has best reduction reaction catalytic activity.
Analyze example 3
This analysis is to utilize linear sweep voltammetry (linear sweep voltammogram) to assess further the electrochemical properties of aforementioned catalyst.During analysis, adopting as analyzed the glassy carbon electrode of example 2 is working electrode, and platinum line is auxiliary electrode, and silver/silver chlorate is reference electrode.And this method is to carry out in the sulfuric acid solution (molal volume concentration is 0.5M) of the 80ml under being full of oxygen atmosphere, the sweep speed of this method is 1mV/s, and scanning direction is for negative.
Refer to Figure 10, preparation example 3,4 and 5 catalyst have obvious reduction wave peak current, and wherein the reduction wave peak current of the catalyst of preparation example 3 is the most obvious.Proving again in these five catalyst, the catalyst of preparation example 3 has best reduction reaction catalytic activity.
Please separately consult Figure 17, the catalyst of preparation example 6 to 10 all has obvious reduction wave peak current, and wherein the reduction wave peak current of the catalyst of preparation example 8 is the most obvious.Proving again in these five catalyst, the catalyst of preparation example 8 has best reduction reaction catalytic activity.
Analyze example 4
This analysis is to utilize the linear sweep voltammetry of collocation rotating disk electrode (r.d.e) (rotating disk electrode) further to assess the electrochemical properties of aforementioned catalyst.During analysis, adopting as analyzed the glassy carbon electrode of example 2 is working electrode, and platinum line is auxiliary electrode, and silver/silver chlorate is reference electrode.And this method is to carry out in the sulfuric acid solution (molal volume concentration is 0.5M) of the 80ml under being full of oxygen atmosphere, the sweep speed of this method is lmV/s, and scanning direction is for negative.
Refer to Figure 11 to Figure 15, the catalyst of preparation example 1 to 5 all has obvious reduction wave peak current under different rotating speeds.Hence one can see that, and these five catalyst all have reduction reaction catalytic activity.
Please separately consult Figure 18 to Figure 22, the catalyst of preparation example 6 to 10 all has obvious reduction wave peak current under different rotating speeds.Hence one can see that, and these five catalyst all have reduction reaction catalytic activity.
Comprehensive above-described embodiment, is illustrating that the method for embodiment of the present invention easily operates and quite saves time, and therefore can facilitate and promptly obtain support type cobalt/cobalt oxide catalyst.
On the other hand, because cobalt ions reacts with chelating agent, form cobalt complex, cobalt ions is present in mixed liquor with the form of cobalt complex, and do not cause attracting each other, excessively do not grow up.Thus, the cobalt/cobalt oxide particle of support type cobalt/cobalt oxide catalyst has the particle diameter of homogeneity, and can allow the electrical efficiency of fuel cell performance optimization, still can reduce the manufacturing cost of fuel cell.
Again on the one hand, support type cobalt/cobalt oxide catalyst is desciccate microwave treatment step and obtaining, and microwave can provide the enough energy of desciccate to destroy desciccate.So, the cobalt/cobalt oxide particle of support type cobalt/cobalt oxide catalyst has the particle diameter of homogeneity, and can allow the electrical efficiency of fuel cell performance optimization, still can reduce the manufacturing cost of fuel cell.
Above are only preferred embodiment of the present invention, but can not limit scope of the invention process with this; Therefore, all simple equivalences of doing according to the present patent application the scope of the claims and description of the invention content change and modify, and all still remain within the scope of the patent.
Claims (10)
1. a manufacture method for catalyst, comprising:
Add cobalt chloride, chelating agent and carbonaceous material to solvent, make the cobalt ions Co in this cobalt chloride
3+react formation with this chelating agent and be adsorbed in the cobalt complex on this carbonaceous material, to make mixed liquor;
Dry this mixed liquor, to obtain desciccate; And
This desciccate of microwave treatment, to form support type cobalt/cobalt oxide catalyst, the cobalt/cobalt oxide particle that this support type cobalt/cobalt oxide catalyst contains carrier and is carried on this carrier.
2. the manufacture method of catalyst as claimed in claim 1, wherein this cobalt/cobalt oxide particle constituting by cobalt black, cobalt sesquioxide, cobaltosic oxide or they.
3. the manufacture method of catalyst as claimed in claim 1, wherein this cobalt complex meets following formula:
[Co (R)
m(H
2o)
n]
3+, wherein R represents this chelating agent, m represents this chelating agent with respect to the molal quantity ratio of this cobalt ions and to be more than or equal to 1, n be H
2o is with respect to the molal quantity ratio of this cobalt ions and be more than or equal to 0, and (ligand number of this chelating agent) * m+n=6.
4. the manufacture method of catalyst as claimed in claim 3, wherein, when the ligand number of this chelating agent is 2, this carrier is CNT.
5. the manufacture method of catalyst as claimed in claim 3, wherein, when the ligand number of this chelating agent is 3,4,5 or 6, this carrier is this carbonaceous material.
6. the manufacture method of the catalyst as described in claim 1,4 or 5, wherein this carbonaceous material is carbon black.
7. the manufacture method of catalyst as claimed in claim 1, wherein this mixed liquor drying steps comprises:
Bestow dehydration means in this mixed liquor, to obtain this desciccate.
8. the manufacture method of catalyst as claimed in claim 7, wherein these dehydration means are bestowed step and are carried out under vacuum environment.
9. the manufacture method of catalyst as claimed in claim 1, wherein the time of this desciccate microwave treatment step is 3 to 30 minutes, and the power output of this microwave is 100 to 3,000W.
10. the manufacture method of catalyst as claimed in claim 1, adds between step and this mixed liquor drying steps at this cobalt chloride, chelating agent and carbonaceous material, comprises further:
Ultrasonic wave stirs this mixed liquor.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935869A (en) * | 2017-03-31 | 2017-07-07 | 扬州大学 | Three-dimensional manometer cobaltosic oxide, preparation method and application |
| CN108654694A (en) * | 2018-07-13 | 2018-10-16 | 南京工业大学 | A kind of carbon nanotube of appendix Fe complexs and its application |
| CN108772101A (en) * | 2018-08-16 | 2018-11-09 | 南京工业大学 | A kind of efficient metal complex molecule catalyst and its preparation and application |
| CN108993609A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | A kind of preparation method and applications of high-dispersion metal catalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101908628A (en) * | 2010-08-18 | 2010-12-08 | 天津久聚能源科技发展有限公司 | Transition metal composite oxide catalytic material and microwave preparation method thereof |
| TW201121982A (en) * | 2009-12-31 | 2011-07-01 | Univ Nat Cheng Kung | Iron complex and methods for making iron complex and supported iron oxide catalyst therethrough |
| CN102324531A (en) * | 2011-05-26 | 2012-01-18 | 东华大学 | Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof |
| CN103170334A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Carbon-supported cobalt oxide catalyst and preparation and application thereof |
| CN103223340A (en) * | 2009-12-31 | 2013-07-31 | 国立成功大学 | Preparation method of ferrousoxide /carrier catalyst |
| CN103331162A (en) * | 2013-06-17 | 2013-10-02 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4/C composite material with high specific surface and crystallization hole wall and preparation method of material |
-
2014
- 2014-07-11 CN CN201410330311.4A patent/CN104162428A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201121982A (en) * | 2009-12-31 | 2011-07-01 | Univ Nat Cheng Kung | Iron complex and methods for making iron complex and supported iron oxide catalyst therethrough |
| CN103223340A (en) * | 2009-12-31 | 2013-07-31 | 国立成功大学 | Preparation method of ferrousoxide /carrier catalyst |
| CN101908628A (en) * | 2010-08-18 | 2010-12-08 | 天津久聚能源科技发展有限公司 | Transition metal composite oxide catalytic material and microwave preparation method thereof |
| CN102324531A (en) * | 2011-05-26 | 2012-01-18 | 东华大学 | Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof |
| CN103170334A (en) * | 2011-12-22 | 2013-06-26 | 中国科学院大连化学物理研究所 | Carbon-supported cobalt oxide catalyst and preparation and application thereof |
| CN103331162A (en) * | 2013-06-17 | 2013-10-02 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4/C composite material with high specific surface and crystallization hole wall and preparation method of material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106935869A (en) * | 2017-03-31 | 2017-07-07 | 扬州大学 | Three-dimensional manometer cobaltosic oxide, preparation method and application |
| CN106935869B (en) * | 2017-03-31 | 2019-04-19 | 扬州大学 | Three-dimensional manometer cobaltosic oxide, preparation method and application |
| CN108654694A (en) * | 2018-07-13 | 2018-10-16 | 南京工业大学 | A kind of carbon nanotube of appendix Fe complexs and its application |
| CN108654694B (en) * | 2018-07-13 | 2020-12-08 | 南京工业大学 | Carbon nanotube loaded with Fe complex and application thereof |
| CN108772101A (en) * | 2018-08-16 | 2018-11-09 | 南京工业大学 | A kind of efficient metal complex molecule catalyst and its preparation and application |
| CN108993609A (en) * | 2018-08-16 | 2018-12-14 | 南京工业大学 | A kind of preparation method and applications of high-dispersion metal catalyst |
| CN108993609B (en) * | 2018-08-16 | 2021-04-06 | 南京工业大学 | Preparation method and application of high-dispersion metal catalyst |
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