CN1170006C - Process for preparing efficient catalytic oxidation-reduction porphyrin/heteropoly acid-modified multi-layer carbon film electrode - Google Patents
Process for preparing efficient catalytic oxidation-reduction porphyrin/heteropoly acid-modified multi-layer carbon film electrode Download PDFInfo
- Publication number
- CN1170006C CN1170006C CNB021164525A CN02116452A CN1170006C CN 1170006 C CN1170006 C CN 1170006C CN B021164525 A CNB021164525 A CN B021164525A CN 02116452 A CN02116452 A CN 02116452A CN 1170006 C CN1170006 C CN 1170006C
- Authority
- CN
- China
- Prior art keywords
- electrode
- porphyrin
- modified
- carbon
- reduction
- 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
Landscapes
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to a preparation method of an efficient catalytic oxygen reduction porphyrin/heteropoly acid multilayer film carbon electrode. The electrocatalytic efficiency of porphyrin to O2 is increased by the synergistically catalytic action of the porphyrin and heteropoly acid. A carbon electrode functionalized by 4-aminobenzoic acid is inserted into a buffer solution containing the porphyrin to be electrochemically scanned, and a porphyrin modified electrode is obtained; after being cleaned, the porphyrin modified electrode is placed in a buffer solution containing the heteropoly acid, circulatory volt-ampere scan is carried out, and the porphyrin/heteropoly acid multilayer film modified carbon electrode is obtained by repeating the two processes. Since the electrode uses covalent pre-modification, the obtained films are stable and orderly and the four electron reduction of oxygen can be realized. The present invention has the advantages of acid resistance and high temperature resistance, and is an ideal material for cathodes of fuel cells.
Description
Technical field: the preparation method of catalytic oxidation-reduction porphyrin/heteropolyacid multi-layer carbon film electrode.
Background technology: along with the develop rapidly and the progress of modernization industry, fuel cell has also obtained flourish.Especially to H
2-O
2The research of fuel cell presses for a kind of energy-efficient cathode catalyst material, thereby realizes that it is to O
2Quadrielectron reduction, avoid intermediate product H
2O
2Generation.Porphyrin and phthalocyanine compound are the oxygen reduction catalysts of using always [Inorg.Chem.1995, Langmuir.1997].But these material great majority can only catalysis O
22 electron reductions generate H
2O
2Or its mixture.It is that face-face dimer Co porphyrin is realized O that Anson group [Anal.Chem.1981] once designed with the dual catalytic agent
24 electron reductions.But this catalyzer instability especially under fuel cell acidity, pyritous working conditions, is easy to decompose.O
2Reduction reaction mainly be to be subjected to the electrode surface structure, i.e. the influence of molecular orientation [J.P.C. (B) 2000,104,3116].Porter once reported porphyrin perpendicular to electrode surface than the porphyrin that lies low to O
2Also original higher catalytic efficiency [Zak, J.; Yuan, H.P.; Ho, M.; Woo, L.K.; Porter, M.D.Langmuir1993,9,2772]. porphyrin fixing on solid material can accurately be controlled its orientation, but bibliographical information method general step is loaded down with trivial details, and the derivatives of porphyrin that needs is difficult synthetic.
The multilayer technique of rising in recent years provides method preferably for the development of Materials science.By layer assembly, can obtain in order, stable, form controlled molecular material.
Summary of the invention: the preparation method who the purpose of this invention is to provide a kind of efficient catalytic oxidation-reduction porphyrin/heteropolyacid multi-layer carbon film electrode.
The object of the present invention is achieved like this, utilizes the concerted catalysis effect of porphyrin and heteropolyacid, thereby improve porphyrin to O
2Reductive electrocatalysis efficient.The carbon dioxide process carbon electrode that is about to the acid functionalization of 4-aminobenzoic is inserted into and carries out electrochemistry scanning in the electrolyte solution that contains porphyrin, obtains the porphyrin multilayer film modified electrode; After the cleaning, put into and contain the heteropolyacid electrolyte solution and carry out electrochemistry scanning.Repeat this two steps process with this, promptly obtain porphyrin/heteropolyacid multilayer film modified electrode.
Because the 4-benzaminic acid is covalently bound on carbon dioxide process carbon electrode, it is stable and be rich in the precursor film of negative charge to make electrode surface obtain one deck.Therefore resulting electrode is more stable, and the growth electrochemistry of porphyrin/heteropolyacid film is controlled, and the film order that obtains is better, is beneficial to realize O
2Quadrielectron reduction, and the favorable reproducibility of multilayer film, and be applicable to assembling on the multiple carbon substrate.
Substrate of the present invention is modified in advance: selecting pre-decorative material is that 4-aminobenzoic acid concentration is 1～100mM, and supporting electrolyte lithium perchlorate concentration is 100mM, and both are dissolved in dehydrated alcohol or the anhydrous acetonitrile simultaneously, and platinized platinum is as counter electrode; In dehydrated alcohol or the anhydrous acetonitrile with Ag/Ag
+Be reference electrode, vitreous carbon, carbon fiber or Graphite Electrodes are as modifying substrate;
Modification step is as follows:
At room temperature clean carbon dioxide process carbon electrode is immersed in the above-mentioned electrolyte solution, in 0～1.4V potential range, carry out cycle potentials scanning under the speed sweeping of 10mV/s, flushing, obtain being rich in the unit molecule precursor film modified graphite electrode of carboxyl functional group, the carbon dioxide process carbon electrode that is modified with this precursor film is immersed in pH=3.3～3.8 in the 100mM acetate buffer solution that contains 0.5～10mM tetramethyl pyridine cobalt porphyrin (CoTMPyP) or tetramethyl pyridine iron porphyrin (FeTMPyP), 0.4～-the 0.4V scope in 10～100mVs
-1The speed of sweeping carry out cyclic voltammetry scan; Take out electrode, after the water flushing, transfer to again and contain 0.5～10mM phosphorus, two tungsten stearic acids and (be called for short P
2W
18) or silicon tungsten laurostearic acid (abbreviation SiW
12) or phosphorus two molybdenum stearic acids (abbreviation P
2Mo
18) the 100mM sulphuric acid soln in 0.3～-the 0.3V scope in 10～100mVs
-1The speed of sweeping carry out cyclic voltammetry scan; Take out electrode, flushing repeats back two steps operation with this, can obtain porphyrin/heteropolyacid multilayer film modified electrode.
But the resulting porphyrin of the present invention/heteropolyacid multi-layer carbon film electrode efficient catalytic oxidation-reduction. with P
2W
18/ CoTMPyP multi-layer carbon film electrode is put in the hac buffer of air saturation pH4.0 can realize O
2Quadrielectron reduction.For SiW
12/ CoTMPyP then realizes O
2Two electron reductions.
Porphyrin of the present invention/heteropolyacid multilayer film modified graphite electrode, the preparation method is simple, quick, easy to operate, modifies mild condition, and required porphyrin and heteropolyacid modifier are commercially available, and raw material is easy to get.And modified membrane is extremely stable, can be used for the research and development of fuel cell oxygen cathode material.Select the heteropolyacid of different structure, the multi-layer carbon film electrode material that makes is to O
2The catalysate difference.Owing to adopt carbon dioxide process carbon electrode, compare with noble metal electrode, the electrochemical window broad, the object that can study is extensive.
Embodiment is as follows:
Embodiment 1:4-benzaminic acid is modified glassy carbon electrode.Clean glassy carbon electrode is put into the ethanol solution of 1mM4-benzaminic acid+100mM lithium perchlorate, use Ag/Ag
+For reference electrode 0～+ the 0.9V potential range in, with the fast cycle potentials scanning of sweeping of 10mV/s 30 minutes, take out electrode washing, make 4-benzaminic acid unitary film modified electrode; Then electrode is put into 0.5mM CoTMPyP+100mM hac buffer pH=3.3 0.4～-the 0.4V scope is with the fast cyclic voltammetry scan of sweeping of 50mV/s, take out and then put into 0.5mM P after electrode water cleans
2W
18In+100mM the sulphuric acid soln 0.3～-carry out cyclic voltammetry scan with the speed of sweeping of 50mV/s in the 0.3V scope, repeat back two steps operation with this and obtain P
2W
18/ CoTMPyP multilayer film electrode.
Embodiment 2:SiW
12/ CoTMPPy multilayer film is modified Graphite Electrodes to O
2Catalytic reduction, the 4-benzaminic acid is modified Graphite Electrodes with embodiment 1; With the modified electrode of 4-benzaminic acid put into 10mMCoTMPPy+100mM hac buffer pH=3.3 0.4～-the 0.4V scope is with the fast cyclic voltammetry scan of sweeping of 100mV/s, take out then put into after electrode water cleans the 10mM+100mM sulphuric acid soln 0.3～-the 0.3V scope carries out cyclic voltammetry scan with the speed of sweeping of 100mV/s, repeats the back operation with this and obtain SiW
12/ CoTMPyP multilayer film electrode.
Embodiment 3:P
2W
18/ FeTMPyP multilayer film modifying carbon fibers electrode pair O
2Catalytic reduction.The 4-benzaminic acid is modified glassy carbon electrode.Clean glassy carbon electrode is put into the anhydrous acetonitrile of 50mM 4-benzaminic acid+100mM lithium perchlorate.Use Ag/Ag
+For reference electrode 0～+ the 0.9V potential range in, with the fast cycle potentials scanning of sweeping of 10mV/s 30 minutes, take out electrode washing; Then 4-benzaminic acid modified electrode is put into 1mM FeTMPyP+100mM hac buffer pH=3.8 0.4～-the 0.4V scope is with the fast cyclic voltammetry scan of sweeping of 10mV/s, take out and then put into 1mMP after electrode water cleans
2W
18In+100mM the sulphuric acid soln 0.3～-carry out cyclic voltammetry scan with the speed of sweeping of 10mV/s in the 0.3V scope, repeat the back operation with this and obtain P
2W
18/ FeTMPyP multilayer film electrode.
Embodiment 4:SiW
12/ FeTMPyP multilayer film modified glassy carbon electrode is to O
2Catalytic reduction.The modification of 4-benzaminic acid is with embodiment same 3.With 4-benzaminic acid electrode put into 4mM FeTMPyP+100mM hac buffer pH=3.8 0.4～-the 0.4V scope is with the fast cyclic voltammetry scan of sweeping of 20mV/s.Take out and then put into 4mM SiW after electrode water cleans
12In+100mM sulfuric acid the buffered soln 0.3～-the 0.3V scope in the fast cyclic voltammetry scan of sweeping of 20mV/s, repeat the back operation with this and obtain SiW
12/ FeTMPyP multilayer film electrode.
Embodiment 5: the anhydrous acetonitrile of clean glassy carbon electrode being put into 100mM 4-benzaminic acid+100mM lithium perchlorate.Use Ag/Ag
+For reference electrode 0～+ the 0.9V potential range in, with the fast cycle potentials scanning of sweeping of 10mV/s 30 minutes, after taking out electrode washing, with 4-benzaminic acid electrode put into 6mM CoTMPyP+100mM hac buffer pH=3.5 0.4V～-the 0.4V scope is with the fast cyclic voltammetry scan of sweeping of 80mV/s; Take out and then put into 6mM P after electrode water cleans
2Mo
18In+100mM sulfuric acid the buffered soln 0.3～-the 0.3V scope in the fast cyclic voltammetry scan of sweeping of 80mV/s, repeat the back operation with this and obtain P
2Mo
18/ CoTMPyP multilayer film electrode.
Embodiment 6:P
2Mo
18/ FeTMPyP multilayer film is modified the catalytic reduction of Graphite Electrodes to oxygen, and the modification of 4-benzaminic acid is with embodiment 5; With 4-benzaminic acid electrode put into 8mM CoTMPyP+100mM hac buffer pH=3.5 0.4V～-the 0.4V scope is with the fast cyclic voltammetry scan of sweeping of 40mV/s.Take out and then put into 8mM P after electrode water cleans
2Mo
18In+100mM sulfuric acid the buffered soln 0.3～-the 0.3V scope in the fast cyclic voltammetry scan of sweeping of 40mV/s, repeat the back operation with this and obtain P
2Mo
18/ FeTMPyP multilayer film electrode.
Claims (1)
1. the preparation method of catalytic oxidation-reduction porphyrin/heteropolyacid multi-layer carbon film electrode, it is characterized in that, substrate is modified in advance: selecting pre-decorative material is that 4-aminobenzoic acid concentration is 1～100mM, supporting electrolyte lithium perchlorate concentration is 100mM, both are dissolved in dehydrated alcohol or the anhydrous acetonitrile simultaneously, and platinized platinum is as counter electrode; In dehydrated alcohol or the anhydrous acetonitrile with Ag/Ag
+Be reference electrode, vitreous carbon, carbon fiber or Graphite Electrodes are as modifying substrate;
Electrode making processes is as follows:
1) at room temperature clean carbon dioxide process carbon electrode is immersed in the above-mentioned electrolyte solution, in 0～1.4V potential range, carries out cycle potentials scanning under the speed, wash, obtain being rich in the unit molecule precursor film modified graphite electrode of carboxyl functional group sweeping of 10mV/s;
2) carbon dioxide process carbon electrode that will be modified with this precursor film is immersed in pH=3.3～3.8 in the 100mM acetate buffer solution that contains 0.5～10mM tetramethyl pyridine cobalt porphyrin or tetramethyl pyridine iron porphyrin, 0.4～-the 0.4V scope in 10～100mV s
-1The speed of sweeping carry out cyclic voltammetry scan; Take out electrode, the water flushing;
3) again with 2) the gained electrode transfer to contain in 0.5～10mM phosphorus, two tungsten stearic acids, silicon tungsten laurostearic acid or the stearic 100mM sulphuric acid soln of phosphorus two molybdenums 0.3～-the 0.3V scope in 10～100mVs
-1The speed of sweeping carry out cyclic voltammetry scan; Take out electrode, flushing;
4) repeat 2), 3) operation of two steps, can obtain porphyrin/heteropolyacid multilayer film modified electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021164525A CN1170006C (en) | 2002-04-05 | 2002-04-05 | Process for preparing efficient catalytic oxidation-reduction porphyrin/heteropoly acid-modified multi-layer carbon film electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021164525A CN1170006C (en) | 2002-04-05 | 2002-04-05 | Process for preparing efficient catalytic oxidation-reduction porphyrin/heteropoly acid-modified multi-layer carbon film electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1386909A CN1386909A (en) | 2002-12-25 |
| CN1170006C true CN1170006C (en) | 2004-10-06 |
Family
ID=4744112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021164525A Expired - Fee Related CN1170006C (en) | 2002-04-05 | 2002-04-05 | Process for preparing efficient catalytic oxidation-reduction porphyrin/heteropoly acid-modified multi-layer carbon film electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1170006C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100380115C (en) * | 2005-01-10 | 2008-04-09 | 厦门大学 | Polymer film modified electrode and preparation method and application thereof |
| US10115972B2 (en) | 2009-04-30 | 2018-10-30 | University Of Florida Research Foundation, Incorporated | Single wall carbon nanotube based air cathodes |
| CN101713760B (en) * | 2009-08-22 | 2012-11-14 | 西北师范大学 | Electrochemical detection method of hydroquinone |
| KR101862432B1 (en) | 2010-12-17 | 2018-05-29 | 유니버시티 오브 플로리다 리서치 파운데이션, 인코포레이티드 | Hydrogen oxidation and generation over carbon films |
| CN102423705B (en) * | 2011-10-17 | 2013-05-01 | 中国科学院山西煤炭化学研究所 | Oxygen reduction catalyst for fuel cell, and preparation method thereof |
| CN103252248A (en) * | 2013-04-24 | 2013-08-21 | 华东师范大学 | Preparation method of ordered mesoporous non-noble-metal-nitrogen-graphitized carbon material |
| WO2015077508A1 (en) * | 2013-11-20 | 2015-05-28 | University Of Florida Research Foundation, Inc. | Carbon dioxide reduction over carbon-containing materials |
| CN105107535A (en) * | 2015-07-14 | 2015-12-02 | 中国科学院长春应用化学研究所 | Self-supporting transition metal-phosphorus alloy catalyst, and preparation method and application thereof |
| CN106108891A (en) * | 2016-06-23 | 2016-11-16 | 中国科学院深圳先进技术研究院 | Microelectrode array that a kind of platinum nano-pillar is modified and preparation method thereof |
| CN106784868A (en) * | 2017-01-10 | 2017-05-31 | 大连理工大学 | A kind of preparation method and application of heteropoly acid/macrocyclic compound/carbon elctro-catalyst |
-
2002
- 2002-04-05 CN CNB021164525A patent/CN1170006C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1386909A (en) | 2002-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sacco | Electrochemical impedance spectroscopy as a tool to investigate the electroreduction of carbon dioxide: A short review | |
| Lee et al. | Immobilization of horseradish peroxidase on multi-wall carbon nanotubes and its electrochemical properties | |
| CN1170006C (en) | Process for preparing efficient catalytic oxidation-reduction porphyrin/heteropoly acid-modified multi-layer carbon film electrode | |
| Wang et al. | One-step unipolar pulse electrodeposition of nickel hexacyanoferrate/chitosan/carbon nanotubes film and its application in hydrogen peroxide sensor | |
| CN106669739A (en) | Transition metal sulfide/carbon nanotube composite material as well as preparation method and application thereof | |
| Kilic et al. | Development and operation of gold and cobalt oxide nanoparticles containing polypropylene based enzymatic fuel cell for renewable fuels | |
| CN114481203A (en) | Foam nickel loaded nanometer flower-shaped nickel sulfide-molybdenum sulfide catalyst, preparation method and application | |
| Yan et al. | Rational functionalization of carbon nanotubes leading to electrochemical devices with striking applications | |
| CN114737215B (en) | Preparation method of nickel-tungsten composite electrode and application of nickel-tungsten composite electrode in electrocatalytic oxidation | |
| Banerjee et al. | A tattoo-like glucose abiotic biofuel cell | |
| CN107195917A (en) | A kind of AuPdNWs superfine nano forest elctro-catalysts of the vertical-growth on FTO glass and preparation method thereof | |
| CN105742651B (en) | A kind of starch biological fuel cell based on glucoamylase Yu the co-modified carbon nanomaterial hydridization anode of nanogold | |
| CN114685802A (en) | Silicon-based covalent organic framework photoelectrode and preparation method and application thereof | |
| CN111777059A (en) | Activation method of carbon nano tube carrier, carbon nano tube carrier and application thereof | |
| US20060234039A1 (en) | Metal-coated carbon surfaces for use in fuel cells | |
| CN101176844B (en) | Direct methanol fuel cell anode catalyzer as well as preparation method and application thereof | |
| CN1303710C (en) | Process for preparing nano structured super platinum film carbon electrodes | |
| CN205355154U (en) | Air negative pole and microbiological fuel cell | |
| CN106268899A (en) | A kind of preparation method of nitrogen-doped graphene Pt-supported catalyst | |
| CN109833835A (en) | A kind of preparation method of the hollow platinum palladium nano-crystal body of inner concave shape, the hollow platinum palladium nano-crystal body of inner concave shape and its application | |
| CN113707891A (en) | Self-supporting electrode substrate material and double-chamber enzyme biofuel cell based on same | |
| CN113036159A (en) | Application of PDMS-based flexible silver nanowire doped graphene/nano nickel platinum composite electrode in fuel cell | |
| CN113130913A (en) | PtNPs/NiNPs/AgNWs/PET plastic electrode and application thereof in construction of fructose fuel cell | |
| CN113013420A (en) | Preparation method of fructose fuel cell with anti-poisoning capacity | |
| Dang et al. | Bias distribution and regulation in photoelectrochemical overall water-splitting cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 |