CN1387273A - Process for preparing methanol-resistant electrocatalyst for cathode of direct methanol fuel battery - Google Patents
Process for preparing methanol-resistant electrocatalyst for cathode of direct methanol fuel battery Download PDFInfo
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Abstract
A carbon carried platinum-transition metal macrocyclic compound composite catalyst with high catalytic oxygen-reducing activity and strong methanol tolerance is prepared through heat treatment at different temp. in an inert gas atmosphere. The catalyst is used as the methanol tolerance cathode electrocatalyst of direct methanol fuel cell.
Description
Technical field: the preparation method who the invention belongs to the direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol.
Background technology: direct methanol fuel cell (DMFC) is removed possesses H
2-O
2Beyond the advantages such as energy conversion efficiency height, the environmental pollution of polymer dielectric film fuel cell (PEMFC) is little, and since abundant, cheap, the easy storage in methyl alcohol source and characteristics such as carry more and more be subject to people's attention now.It most possibly at first is applied in such as on the miniaturized electronicss such as mobile phone, field camera, notebook computer.But the research of DMFC also exists the problem of " methyl alcohol penetrate " at present, be that methyl alcohol passes dielectric film from anode and is diffused into negative electrode, owing to carry out in the time of hydrogen reduction and methanol oxidation, produce " mixed potential ", and methyl alcohol and accessory substance thereof also can make cathod catalyst poison, and seriously reduce the efficient of fuel and the power output of battery.One of method that addresses this problem is the good electrocatalyst for cathode of development selectivity, and promptly catalyst only has activity to hydrogen reduction, and the methanol oxidation non-activity is not poisoned by methyl alcohol.
Up to now, people to study maximum PEMFC electrocatalyst for cathode be platinum and alloy [Mukerjee S., Srinivasan S., J.Electroanal.Chem., 1993,357:201-224; Toda T., Igarashi H., Uchida H.J, et al., Electrochem.Soc., 1999,146:3750-3756], also have in addition: the porphyrin of (1) transition metal macrocyclic compound, especially Fe and Co and phthalocyanine compound [Faubert G., Cote R., Guay D.et al., Electrochim.Acta., 1998,43 (3-4): 341-353]; (2) have perovskite, the isostructural transition metal oxide of pyrochlore, but their instabilities [Egdell R.G., Goodenough J.B., Hamnett A.etal., J.Chem.Soc.Faraday Trans., 1983, I79:893-912] in acid solution; (3) transition metal atoms cluster compound [Alonso-Vante N., Schubert B., Tributsch H., Mater.Chem.Phys., 1989,22:281-307].Platinum and alloy as catalyst hydrogen reduction thereof active higher, but its anti-methyl alcohol poor ability; Though and the anti-methyl alcohol ability of other non-platinum catalyst is stronger, active and stability differs bigger with platinum based catalyst.Along with DMFC to the further developing of practicability and commercialization direction, the problem of relevant " methyl alcohol penetrate " will be more and more outstanding, therefore, the development of the active height of catalytic oxidation-reduction, electrocatalyst for cathode that anti-methyl alcohol ability is strong will more and more be subject to people's attention.
Summary of the invention: the preparation method who the purpose of this invention is to provide a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol.
Platinum and transition metal macrocyclic compound all have advantages of high catalytic activity to hydrogen reduction; and the character that easily distils when transition metal macrocyclic compound also has good anti-methyl alcohol ability and high temperature; the two is made charcoal carry composite catalyst; and under inert gas shielding, heat-treat in different temperatures, can obtain the active height of a class catalytic oxidation-reduction, carbon supported platinum-transition metal macrocyclic compound composite catalyst that anti-methyl alcohol ability is strong.This is because in composite catalyst, the electron distributions state of platinum and transition metal macrocyclic compound and molecular structure interaction has further improved separately the catalytic activity to hydrogen reduction; In addition, transition metal macrocyclic compound is at the special dispersing mode on platinum surface, make the active sites on platinum surface to interact, and methyl alcohol can't contact because the molecule steric hindrance is big with the active sites of platinum, so improved the anti-methyl alcohol performance of catalyst with the less oxygen of molecular structure.
The transition metal macrocyclic compound that the present invention selects is to be respectively porphyrin, phthalocyanine, uncommon furan alkali, annulene and the derivative thereof of central metal ion with chromium, molybdenum, manganese, iron, cobalt, nickel, ruthenium, rhodium, iridium, platinum, copper; The organic solvent of selecting is N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide, n-hexane, carrene, chloroform, tetrachloromethane, ethanol, isopropyl alcohol, ether, acetone, pyridine or oxolane; The reducing agent of selecting for use is formaldehyde, formic acid, hydrazine hydrate, sodium borohydride or potassium borohydride; In solution, the content of active carbon is 0.1-1g/L, and the content of platinum is 0.05-1g/L, and the content of transition metal macrocyclic compound is 0.02-1g/L; The mass ratio of platinum and transition metal macrocyclic compound is 0.1-10.
Preparation process has three kinds of modes:
(1) is that the charcoal of 5-50% carries platinum and joins in the organic solvent with the quality percentage composition, stirs, slowly add transition metal macrocyclic compound then, stir, slowly add the 0-5000 ml deionized water again, continue to stir;
(2) be that the carbon-supported transitional metal macrocyclic compound of 5-50% joins in the deionized water with the quality percentage composition, stir, slowly add chloroplatinic acid aqueous solution then, stir, and to regulate the pH value with sodium bicarbonate solution be 8-10, stir, add the excessive 2.5-5 of the molal quantity reducing agent doubly of relative platinum, continue to stir;
(3) active carbon is joined in the organic solvent, stir, slowly add the mixed organic solvents of chloroplatinic acid and transition metal macrocyclic compound then, stir, add the excessive 2.5-5 of the molal quantity reducing agent doubly of relative platinum, stir, slowly add the 0-5000 ml deionized water, continue to stir;
The catalyst that makes is filtered, and the precipitate with deionized water washing is 80 ℃ of following vacuumizes.And with catalyst under 100-1100 ℃ of argon shield heat treatment 1-3 hour.
The carbon supported platinum-transition metal macrocyclic compound composite catalyst of the present invention's preparation is compared with existing oxygen reduction cathode eelctro-catalyst, and the preparation method is simple; Catalytic oxidation-reduction is active high; Anti-methyl alcohol ability is strong.Obtained by the cathodic polarization curve that records: with identical on platinum, and in whole potential range, the former reduction current equals even greater than platinum oxygen at the take-off potential that reduces on the composite catalyst; When methyl alcohol existed, the reduction of oxygen on composite catalyst was unaffected substantially.
Embodiment is as follows:
Embodiment 1: with the quality percentage composition of platinum is that 20% 250mg charcoal carries platinum and joins in 250 milliliters of acetone; stirred 6 hours; slowly add the 25mg ferriporphyrin then; stirred 6 hours, and slowly added the 500mL deionized water again, continue to stir 6 hours; filter; with deionized water wash three times, 80 ℃ of following vacuumizes, at last with catalyst heat treatment 2 hours under 450 ℃ of argon shields.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.83V (with respect to standard hydrogen electrode), and be identical with corresponding charcoal platinum catalyst, is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/5; When methyl alcohol existed, oxygen carried reduction take-off potential decline 0.13V on the platinum at charcoal, and the 0.03V that only descends on composite catalyst is the 0.55V place at current potential, and the latter's electric current is the former 1.57 times.
Embodiment 2: other condition is with embodiment 1, and the quality percentage composition that only changes platinum is 5%, and organic solvent is N, dinethylformamide, transition metal macrocyclic compound are the 12.5mg iron-phthalocyanine, and deionized water is 250mL, heat treatment temperature is 700 ℃, and the time is 1 hour.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 3: other condition is with embodiment 1, and the quality percentage composition that only changes platinum is 10%, and organic solvent is N, N-dimethylacetylamide, transition metal macrocyclic compound are 125mg iron-tetramethoxy porphyrin, and deionized water is 2500mL, heat treatment temperature is 1000 ℃, and the time is 1 hour.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.80V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/10; When methyl alcohol existed, the reduction take-off potential of oxygen on composite catalyst do not change, and is the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.3 times at the reduction current on the composite catalyst.
Embodiment 4: other condition is with embodiment 1, and the quality percentage composition that only changes platinum is 30%, and organic solvent is an anhydrous pyridine, and transition metal macrocyclic compound is a 7.5mg cobalt phthalocyanine, and deionized water is 100mL, and heat treatment temperature is 1100 ℃, and the time is 1 hour.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/9; When methyl alcohol existed, the reduction take-off potential of oxygen on composite catalyst do not change, and is the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.1 times at the reduction current on the composite catalyst.
Embodiment 5: other condition is with embodiment 1, and the quality percentage composition that only changes platinum is 50%, and organic solvent is an isopropyl alcohol, and transition metal macrocyclic compound is a 15.625mg cobalt porphyrin, and deionized water is 200mL, and heat treatment temperature is 600 ℃, and the time is 3 hours.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/7; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.4 times at the reduction current on the composite catalyst.
Embodiment 6: other condition is with embodiment 1, and only changing organic solvent is carrene, and transition metal macrocyclic compound is 10mg iron-tetraphenyl phthalocyanine, and deionized water is 150mL, and heat treatment temperature is 800 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/8; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.3 times at the reduction current on the composite catalyst.
Embodiment 7: other condition is with embodiment 1, and the quality percentage composition that only changes platinum is 10%, and organic solvent is a methyl-sulfoxide, transition metal macrocyclic compound is 250mg iron-dibenzo-four azepine annulene, deionized water is 5000mL, and heat treatment temperature is 300 ℃, and the time is 3 hours.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/5; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.5 times at the reduction current on the composite catalyst.
Embodiment 8: other condition only is after the mixed organic solvents that charcoal is carried platinum and cobalt-tetracarboxylic phthalocyanine stirs 6 hours with embodiment 1, does not add deionized water, Direct Filtration.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.6 times at the reduction current on the composite catalyst.
Embodiment 9: with the quality percentage composition of iron-tetrasulfonic acid base porphyrin is that 20% 250mg charcoal carries iron-tetrasulfonic acid base porphyrin and joins in the 500mL deionized water, stirred 6 hours, add the platinum acid chloride solution that platinum content is 20mg then, stirred 6 hours, and added sodium bicarbonate aqueous solution and regulate pH=9, stirred 2 hours, add the 136mg sodium borohydride, continue to stir 6 hours, filter, precipitate with deionized water is washed to filtrate does not have Cl
-Till, 80 ℃ of following vacuumizes, at last with catalyst heat treatment 2 hours under 700 ℃ of argon shields.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/5; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.01V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.3 times at the reduction current on the composite catalyst.
Embodiment 10: other condition is with embodiment 9, and only changing the carbon-supported transitional metal macrocyclic compound is 20% 50mg platinum phthalocyanine for the quality percentage composition, and the content of platinum is 15mg in the platinum acid chloride solution, and reducing agent is a 9.2mg formaldehyde, and heat treatment temperature is 900 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.80V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 11: other condition is with embodiment 9, and only changing the carbon-supported transitional metal macrocyclic compound is that 50% charcoal carries the manganese phthalocyanine for the quality percentage composition, and the content of platinum is 12.5mg in the platinum acid chloride solution, and reducing agent is the 16mg hydrazine hydrate, and heat treatment temperature is 800 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/5; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.1 times at the reduction current on the composite catalyst.
Embodiment 12: other condition is with embodiment 9, and only changing the carbon-supported transitional metal macrocyclic compound is that 30% charcoal carries nickel-tetraphenylporphyrin for the quality percentage composition, and the content of platinum is 50mg in the platinum acid chloride solution, and reducing agent is a 46mg formaldehyde, and heat treatment temperature is 300 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/4; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 13: other condition is with embodiment 9, only changing the carbon-supported transitional metal macrocyclic compound is that 8% charcoal carries iridium-octaethylporphyrin for the quality percentage composition, the content of platinum is 120mg in the platinum acid chloride solution, and reducing agent is the 150mg potassium borohydride, and heat treatment temperature is 500 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 14: the 500mg active carbon is joined in the 500mL acetone, stirred 6 hours, slowly the adding platinum content is that chloroplatinic acid and the ruthenium-phthalocyanine content of 80mg are the acetone soln 100mL of 20mg, stirred 6 hours, add 94mg formic acid and reduce, continue to stir 1 hour, slowly add the 400mL deionized water, filter, precipitate with deionized water is washed to filtrate does not have Cl
-Till, 60 ℃ of following vacuumizes, at last with catalyst heat treatment 2 hours under 100 ℃ of argon shields.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/4; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.04V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 15: other condition is with embodiment 14, and only changing organic solvent is ethanol, and platinum content is the chloroplatinic acid of 50mg, transition metal macrocyclic compound is rhodium-tetraphenyl phthalocyanine of 200mg, and reducing agent is a 27mg formaldehyde, does not add deionized water after the reduction, Direct Filtration, heat treatment temperature are 400 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 16: other condition is with embodiment 14, and only changing organic solvent is chloroform, and platinum content is the chloroplatinic acid of 20mg, transition metal macrocyclic compound is 40mg chromium-tetrasulfonic acid base phthalocyanine, reducing agent is a 28.3mg formic acid, and deionized water is 800mL, and heat treatment temperature is 900 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.01V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 17: other condition is with embodiment 14, and only changing organic solvent is tetrachloromethane, and platinum content is the chloroplatinic acid of 150mg, transition metal macrocyclic compound is molybdenum-naphthalene phthalocyanine of 187.5mg, reducing agent is a 159mg formic acid, and deionized water is 350mL, and heat treatment temperature is 700 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.82V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/5; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.3 times at the reduction current on the composite catalyst.
Embodiment 18: other condition is with embodiment 14, and only changing organic solvent is n-hexane, and platinum content is the chloroplatinic acid of 200mg, transition metal macrocyclic compound is copper-phthalocyanine of 50mg, reducing agent is the 282mg hydrazine hydrate, and deionized water is 800mL, and heat treatment temperature is 550 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.83V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.03V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Embodiment 19: other condition is with embodiment 14, and only changing organic solvent is oxolane, and platinum content is the chloroplatinic acid of 100mg, transition metal macrocyclic compound is the uncommon furan alkali of the manganese of 80mg, reducing agent is a 74mg formaldehyde, and deionized water is 1750mL, and heat treatment temperature is 750 ℃.Obtained by cathodic polarization curve, the reduction take-off potential of oxygen on composite catalyst is 0.81V (with respect to standard hydrogen electrode), is the 0.55V place at current potential, and the corresponding charcoal platinum catalyst of hydrogen reduction current ratio has increased by 1/6; When methyl alcohol existed, the reduction take-off potential of oxygen on the composite catalyst 0.02V that only descends was the 0.55V place at current potential, and oxygen is on corresponding platinum catalyst 1.2 times at the reduction current on the composite catalyst.
Claims (7)
1. the preparation method of the direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol is characterized in that the transition metal macrocyclic compound of selecting is is respectively porphyrin, phthalocyanine, uncommon furan alkali, annulene and the derivative thereof of central metal ion with chromium, molybdenum, manganese, iron, cobalt, nickel, ruthenium, rhodium, iridium, platinum, copper; The organic solvent of selecting is N, dinethylformamide, N, N-dimethylacetylamide, methyl-sulfoxide, n-hexane, carrene, chloroform, tetrachloromethane, ethanol, isopropyl alcohol, ether, acetone, pyridine or oxolane; The reducing agent of selecting for use is formaldehyde, formic acid, hydrazine hydrate, sodium borohydride or potassium borohydride; In solution, the content of active carbon is 0.1-1g/L, and the content of platinum is 0.05-1g/L, and the content of transition metal macrocyclic compound is 0.02-1g/L; The mass ratio of platinum and transition metal macrocyclic compound is 0.1-10;
Preparation process has three kinds of modes:
(1) is that the charcoal of 5-50% carries platinum and joins in the organic solvent with the quality percentage composition, stirs, slowly add transition metal macrocyclic compound then, stir, slowly add the 0-5000 ml deionized water again, continue to stir;
(2) be that the carbon-supported transitional metal macrocyclic compound of 5-50% joins in the deionized water with the quality percentage composition, stir, slowly add chloroplatinic acid aqueous solution then, stir, and to regulate the pH value with sodium bicarbonate solution be 8-10, stir, add the excessive 2.5-5 of the molal quantity reducing agent doubly of relative platinum, continue to stir;
(3) active carbon is joined in the organic solvent, stir, slowly add the mixed organic solvents of chloroplatinic acid and transition metal macrocyclic compound then, stir, add the excessive 2.5-5 of the molal quantity reducing agent doubly of relative platinum, stir, slowly add the 0-5000 ml deionized water, continue to stir;
The catalyst that makes is filtered, the precipitate with deionized water washing, 80 ℃ of following vacuumizes, and with catalyst under 100-1100 ℃ of argon shield heat treatment 1-3 hour.
2. the preparation method of a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol as claimed in claim 1 is characterized in that the transition metal macrocyclic compound selected is for being central metal ion with chromium, molybdenum, manganese, iron, cobalt, nickel, ruthenium, rhodium, iridium, platinum or copper respectively.
3. the preparation method of a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol as claimed in claim 1 is characterized in that the transition metal macrocyclic compound of selecting is is respectively porphyrin, phthalocyanine, uncommon furan alkali, annulene and the derivative thereof of central metal ion with chromium, molybdenum, manganese, iron, cobalt, nickel, ruthenium, rhodium, iridium, platinum or copper.
4. the preparation method of a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol as claimed in claim 1 is characterized in that described derivative is the tetramethoxy porphyrin, tetrasulfonic acid base porphyrin, tetraphenylporphyrin, octaethylporphyrin.
5. the preparation method of a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol as claimed in claim 1 is characterized in that described derivative is the tetraphenyl phthalocyanine, tetracarboxylic phthalocyanine, tetrasulfonic acid base phthalocyanine, naphthalene phthalocyanine.
6. the preparation method of a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol as claimed in claim 1 is characterized in that described derivative is dibenzo-four an azepine annulene.
7. the preparation method of a kind of direct methanol fuel cell electrocatalyst for cathode of anti-methyl alcohol as claimed in claim 1, the mass ratio that it is characterized in that platinum and transition metal macrocyclic compound is 0.1-10.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1299377C (en) * | 2003-12-31 | 2007-02-07 | 山东理工大学 | Application of products with active carbon surface chemically decorated by porphyrin and phthalocyanine in fuel cells |
| CN1300879C (en) * | 2004-10-20 | 2007-02-14 | 华南理工大学 | Fuel cell anode catalyst using heteropolyacid as promoter and preparation method thereof |
| CN100386910C (en) * | 2006-06-09 | 2008-05-07 | 武汉理工大学 | Efficient direct methyl alcohol fuel battery negative pole catalyst and producing method thereof |
| CN100433413C (en) * | 2005-12-31 | 2008-11-12 | 山东理工大学 | Weak alkaline polymer membrane direct alcohols fuel cell |
| CN104624190A (en) * | 2013-11-12 | 2015-05-20 | 华中科技大学 | Cobalt-based transition metal oxygen reduction catalyst, preparation method and application thereof |
| CN104998658A (en) * | 2015-07-20 | 2015-10-28 | 昆明贵研催化剂有限责任公司 | Method for preparing proton-exchange membrane fuel cell oxygen reduction catalyst based on PtNi (111) octahedral single crystal nanoparticles |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1299377C (en) * | 2003-12-31 | 2007-02-07 | 山东理工大学 | Application of products with active carbon surface chemically decorated by porphyrin and phthalocyanine in fuel cells |
| CN1300879C (en) * | 2004-10-20 | 2007-02-14 | 华南理工大学 | Fuel cell anode catalyst using heteropolyacid as promoter and preparation method thereof |
| CN100433413C (en) * | 2005-12-31 | 2008-11-12 | 山东理工大学 | Weak alkaline polymer membrane direct alcohols fuel cell |
| CN100386910C (en) * | 2006-06-09 | 2008-05-07 | 武汉理工大学 | Efficient direct methyl alcohol fuel battery negative pole catalyst and producing method thereof |
| CN104624190A (en) * | 2013-11-12 | 2015-05-20 | 华中科技大学 | Cobalt-based transition metal oxygen reduction catalyst, preparation method and application thereof |
| CN104998658A (en) * | 2015-07-20 | 2015-10-28 | 昆明贵研催化剂有限责任公司 | Method for preparing proton-exchange membrane fuel cell oxygen reduction catalyst based on PtNi (111) octahedral single crystal nanoparticles |
| CN106654307A (en) * | 2017-01-10 | 2017-05-10 | 大连理工大学 | Preparation method and application of noble metal@graphite layer core-shell structured electro-catalyst |
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