CN1052117C - Preparation of electrode of higher stably catalyzing redox by using thermal dressing method - Google Patents
Preparation of electrode of higher stably catalyzing redox by using thermal dressing method Download PDFInfo
- Publication number
- CN1052117C CN1052117C CN95104915A CN95104915A CN1052117C CN 1052117 C CN1052117 C CN 1052117C CN 95104915 A CN95104915 A CN 95104915A CN 95104915 A CN95104915 A CN 95104915A CN 1052117 C CN1052117 C CN 1052117C
- Authority
- CN
- China
- Prior art keywords
- electrode
- tetraphenylporphyrin
- make
- glassy carbon
- quartz ampoule
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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 present invention belongs to the preparation of an electrode with highly stable catalytic oxygen reduction by a heat modification method. Meso-tetraphenylporphyrin iron (III) chloride complex (or cobalt) is used as a catalyst; heat modification is applied to metalloporphyrin on the surface of vitreous carbon, and an activity catalyzing center is attached to the electrode by a one-step method. The obtained electrode has high catalytic activity and stability to an oxygen reduction reaction.
Description
The invention belongs to the hot repair decorations method of preparation high stable catalytic oxidation-reduction electrode.
The Metallomacrocycle complex has very high catalytic activity to the reduction reaction of oxygen, is possible substitute noble metal platinum to realize normal temperature fuel cell material likely as catalyst.But, this compounds is very unstable to the catalysis of oxygen, if this class complex is adsorbed on the activity carbon carrier, in inert atmosphere, carry out high-temperature heat treatment and can improve its catalytic stability, after heat treatment obtain a kind of grained catalyst, because it is water insoluble and organic solvent fully, it is very difficult to make practical electrode.International Electroanalytical Chemistry magazine 205,233 (1986) discloses the influence that the cracking transition metal chelate reduces to molecular oxidation on the carbon support, and domestic Wuhan University journal has also been delivered through the catalytic action of heat treated porphyrin compound to the oxygen electrode reaction.But because the porousness and the roughness on powdered granule surface, prepared electrode can not be used for the research and the sign of catalytic oxidation-reduction.
The objective of the invention is on the vitreous carbon surface metalloporphyrin to be carried out the hot repair decorations, with one-step method the active catalytic center is followed on electrode, gained electrode pair oxygen reduction reaction has high catalytic activity and stability.
The present invention selects for use tetraphenylporphyrin iron or tetraphenylporphyrin cobalt to make catalyst, adopts vitreous carbon to make electrode material, and the preparation method is with glassy carbon electrode soaked overnight in the concentrated sulfuric acid of potassium bichromate, cleans, with 300 order MgO or 1 μ m α-Al
2O
3With the vitreous carbon surface finish, place the glassy carbon electrode surface with 0.5g～0.2g FeTPP powder or CoTPP powder, grind mutually with the smooth surface of another piece glassy carbon electrode, make it evenly, closely be distributed on two plate electrodes; The glassy carbon electrode that coats is lain against in the little quartz ampoule, at N
2Put sealing cap in the gas, make it that sealing be arranged, in addition with the logical N of the big quartz ampoule in the tube furnace
2After, the little quartz ampoule that seals is placed in one, at N
2Average rate is warming up to 500 ℃～800 ℃ under the gas shiled, and constant temperature 0.5～2 hour is cooled to room temperature, takes out and uses the distilled water cleaning, drying, makes tetraphenylporphyrin iron or the tetraphenylporphyrin cobalt chemically modified electrode Fe TPP/GC or the Co TPP/GC of hot repair decorations.
To be fixed on the tetraphenylporphyrin iron on glassy carbon electrode surface through one hour resulting electrode Fe TPP/GC of 500 ℃ of hot repair decorations, stability to the catalytic reduction molecular oxygen is very high, its catalysis peak occurs in+the 0.05V place, through continuous 1000 current potential scan rounds, the electric current of catalytic oxidation-reduction is constant substantially, and is higher 2 more than the order of magnitude than the data of report in the past.
Tetraphenylporphyrin iron or tetraphenylporphyrin cobalt are adornd resulting electrode at 0.05mol/L H through 800 ℃ of hot repairs
2SO
4In through continuous 3000 current potential scan rounds, the peak current of catalytic molecular hydrogen reduction is constant, and is extremely stable.
Use mass spectral analysis, proved around tetraphenylporphyrin iron or tetraphenylporphyrin cobalt have lost in the heating modification four phenyl ring Mossbuar spectrum proofs only remaining in N
4Ring and central metal iron or cobalt atom have kept catalytic activity, between the C atom with N atom in the ESCA proof dressing agent and electrode surface the chemical bonding effect have taken place.
Embodiment provided by the invention is as follows:
Embodiment 1: get glassy carbon electrode soaked overnight, clean in the concentrated sulfuric acid of potassium bichromate, with 300 order MgO with the vitreous carbon surface finish, place the glassy carbon electrode surface with 0.5gFe TPP powder, smooth surface with another sheet glass carbon electrode grinds mutually, make it evenly, closely be distributed on the surface of two plate electrodes, the glassy carbon electrode that coats is lain against in the little quartz ampoule, at N
2Put sealing cap in the gas, make it that certain sealing be arranged, in addition with the logical N of the big quartz ampoule in the tube furnace
2After, the little quartz ampoule that seals is placed in one, at N
2Average rate is warming up to 500 ℃ under the gas shiled, and constant temperature 1 hour is cooled to room temperature, takes out and uses the distilled water cleaning, drying, makes the tetraphenylporphyrin iron chemically modified electrode of hot repair decorations.
Embodiment 2: with α-Al of 1 μ m
2O
3With the vitreous carbon surface finish, grind between two glass carbon plates with the 0.2gCoTPP powder, be warming up to 600 ℃, constant temperature 1.5 hours, all the other steps obtain heat treated tetraphenylporphyrin cobalt chemically modified electrode with embodiment 1.
Embodiment 3: with the vitreous carbon surface finish,, be warming up to 550 ℃ with 300 order MgO with 0.5gFe TPP powder, and constant temperature 0.5 hour, all the other steps obtain heat treated tetraphenylporphyrin iron chemically modified electrode with embodiment 1.
Embodiment 4: with α-Al of 1 μ m
2O
3With the vitreous carbon surface finish, with 0.4gCo TPP powder, be warming up to 800 ℃, constant temperature 1 hour, all the other steps obtain heat treated tetraphenylporphyrin cobalt chemically modified electrode with embodiment 1.
Claims (1)
1. method is adornd in a hot repair for preparing high stable catalytic oxidation-reduction electrode, it is characterized in that selecting for use tetraphenylporphyrin iron or tetraphenylporphyrin cobalt to make catalyst, adopt vitreous carbon to make electrode material, the preparation method is with glassy carbon electrode soaked overnight in the concentrated sulfuric acid of potassium bichromate, clean, with 300 order MgO or 1 μ m α-Al
2O
3With the vitreous carbon surface finish, place the glassy carbon electrode surface with 0.5g～0.2g FeTPP powder or CoTPP powder, grind mutually with the smooth surface of another piece glassy carbon electrode, make it even, closely be distributed on the surface of two plate electrodes; The glassy carbon electrode that coats is lain against in the little quartz ampoule, at N
2Put sealing cap in the gas, make it that sealing be arranged, in addition with the logical N of the big quartz ampoule in the tube furnace
2After, the little quartz ampoule that seals is placed in one, at N
2Average rate is warming up to 500 ℃～800 ℃ under the gas shiled, and constant temperature 0.5～2 hour is cooled to room temperature, takes out and uses the distilled water cleaning, drying, makes tetraphenylporphyrin iron or the tetraphenylporphyrin cobalt chemically modified electrode FeTPP/GC or the CoTPP/GC of hot repair decorations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95104915A CN1052117C (en) | 1995-05-10 | 1995-05-10 | Preparation of electrode of higher stably catalyzing redox by using thermal dressing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95104915A CN1052117C (en) | 1995-05-10 | 1995-05-10 | Preparation of electrode of higher stably catalyzing redox by using thermal dressing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135664A CN1135664A (en) | 1996-11-13 |
| CN1052117C true CN1052117C (en) | 2000-05-03 |
Family
ID=5075307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95104915A Expired - Fee Related CN1052117C (en) | 1995-05-10 | 1995-05-10 | Preparation of electrode of higher stably catalyzing redox by using thermal dressing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1052117C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1303710C (en) * | 2005-04-05 | 2007-03-07 | 中国科学院长春应用化学研究所 | Process for preparing nano structured super platinum film carbon electrodes |
| CN102056861A (en) * | 2008-06-09 | 2011-05-11 | 原子能和代替能源委员会 | Electrode for lead-acid battery and method for producing such an electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991001806A1 (en) * | 1989-08-10 | 1991-02-21 | Societe Nationale Elf Aquitaine | Oxidation catalysts based on metalloporphyrine on a substrate |
| WO1991001985A1 (en) * | 1989-08-10 | 1991-02-21 | Societe Nationale Elf Aquitaine | Substituted phenyl meso-tetraphenyl porphyrins |
-
1995
- 1995-05-10 CN CN95104915A patent/CN1052117C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991001806A1 (en) * | 1989-08-10 | 1991-02-21 | Societe Nationale Elf Aquitaine | Oxidation catalysts based on metalloporphyrine on a substrate |
| WO1991001985A1 (en) * | 1989-08-10 | 1991-02-21 | Societe Nationale Elf Aquitaine | Substituted phenyl meso-tetraphenyl porphyrins |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1135664A (en) | 1996-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kawai et al. | Photocatalytic decomposition of gaseous water over TiO2 and TiO2—RuO2 surfaces | |
| Grodkowski et al. | Reduction of cobalt and iron phthalocyanines and the role of the reduced species in catalyzed photoreduction of CO2 | |
| Rakap et al. | Polymer-immobilized palladium supported on TiO2 (Pd–PVB–TiO2) as highly active and reusable catalyst for hydrogen generation from the hydrolysis of unstirred ammonia–borane solution | |
| CN101175570A (en) | Porphyrin-based electrode catalyst | |
| CN109776814A (en) | A kind of acid imide covalent organic frame material and its preparation method and application | |
| CN101024188A (en) | Halogen-oxide photocatalytic material and preparing method | |
| CN110538657B (en) | Iron-nickel layered double hydroxide and preparation method and application thereof | |
| Beley et al. | Electrochemical regeneration of nicotinamide cofactor using a polypyrrole rhodium bis-terpyridine modified electrode | |
| CZ67895A3 (en) | Purification process of inert gases | |
| Xu et al. | In situ cofactor regeneration enables selective CO2 reduction in a stable and efficient enzymatic photoelectrochemical cell | |
| CN1052117C (en) | Preparation of electrode of higher stably catalyzing redox by using thermal dressing method | |
| JPH08301606A (en) | Production of oxygen and hydrogen | |
| CN101327425A (en) | Method for preparing nitrogen-doped titanium dioxide photocatalyst | |
| CN113546661A (en) | Carbon-based single-atom photocatalyst and preparation method and application thereof | |
| CN110255697B (en) | Preparation of nitrogen-doped carbon anode and application of nitrogen-doped carbon anode in catalytic wet air oxidation | |
| Shen et al. | Fabrication of Metalloporphyrin‐Polyoxometalyte Hybrid Film by Layer‐by‐Layer Method and Its Catalysis for Dioxygen Reduction | |
| CN110639490A (en) | Preparation method and application of porous carbon-based nitrogen reduction catalyst | |
| Ehrensberger et al. | Production of carbon from carbon dioxide with iron oxides and high-temperature solar energy | |
| CN100411732C (en) | Method for preparing nano powder catalyst | |
| CN114628707A (en) | Modified carbon brush cathode material for microbial electro-Fenton fuel cell and preparation method and application thereof | |
| JPS62120489A (en) | Indirect electrochemical reduction of carbon dioxide at ordinary temperature and pressure | |
| CN114481188B (en) | Preparation method of surface nitrogen-doped electrode | |
| CN101480615A (en) | Catalyst for decomposing laughing gas and preparation method thereof | |
| EP1785187A1 (en) | Catalyst for water gas shift reaction and preparation method thereof | |
| CN114733507B (en) | Carbon nano tube coated diamond nickel particle catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |