CN1386909A - 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
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- CN1386909A CN1386909A CN02116452.5A CN02116452A CN1386909A CN 1386909 A CN1386909 A CN 1386909A CN 02116452 A CN02116452 A CN 02116452A CN 1386909 A CN1386909 A CN 1386909A
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- porphyrin
- reduction
- heteropolyacid
- catalytic oxidation
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Abstract
A carbon electrode with porphyrin/heteropoly acid multi layer film for efficient catalytic reduction of oxygen is prepared from carbon electrode through inserting it in buffer solution containing porphyrin, electrochemical scanning to obtain porphyrin modified electrode, washing, inserting in buffer solution containing heteropoly acid, cyclic V-A scanning and repeating said steps. Its advantages are stable and ordered film, and high resistance to acid and high temp. It can be used as cathode of fuel battery.
Description
Technical field: the preparation method of efficient 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
+Being reference electrode, is reference electrode with Ag/AgCl in the aqueous solution; 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 10～100mV s
-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 10～100mV s
-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
10/ 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 (7)
1. the preparation method of efficient 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
+Being reference electrode, is reference electrode with Ag/AgCl in the aqueous solution; 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.
2. the preparation method of efficient catalytic oxidation-reduction porphyrin as claimed in claim 1/heteropolyacid multi-layer carbon film electrode is characterized in that the unit molecule precursor film modified graphite electrode that will be rich in carboxyl functional group is immersed in picoline cobalt porphyrin.
3. the preparation method of efficient catalytic oxidation-reduction porphyrin as claimed in claim 1/heteropolyacid multi-layer carbon film electrode is characterized in that the unit molecule precursor film modified graphite electrode that will be rich in carboxyl functional group is immersed in the tetramethyl pyridine iron porphyrin.
4. the preparation method of efficient catalytic oxidation-reduction porphyrin as claimed in claim 1/heteropolyacid multi-layer carbon film electrode is characterized in that 2) the gained electrode transfers in the sulphuric acid soln of phosphorus two tungsten 18.
5. the preparation method of efficient catalytic oxidation-reduction porphyrin as claimed in claim 1/heteropolyacid multi-layer carbon film electrode is characterized in that 2) the gained electrode transfers in the sulphuric acid soln of silicon tungsten laurostearic acid.
6. the preparation method of efficient catalytic oxidation-reduction porphyrin as claimed in claim 1/heteropolyacid multi-layer carbon film electrode is characterized in that 2) the gained electrode transfers in phosphorus two molybdenums 18 sulphuric acid solns.
7. the preparation method of efficient catalytic oxidation-reduction porphyrin as claimed in claim 1/heteropolyacid multi-layer carbon film electrode is characterized in that selecting tetramethyl pyridine cobalt porphyrin or tetramethyl pyridine iron porphyrin and phosphorus two tungsten 18, silicon tungsten 12 or phosphorus two molybdenums 18 to carry out multiple modification.
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| CN1170006C CN1170006C (en) | 2004-10-06 |
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Cited By (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 |
| CN102423705A (en) * | 2011-10-17 | 2012-04-25 | 中国科学院山西煤炭化学研究所 | Oxygen reduction catalyst for fuel cell, and preparation method thereof |
| CN101713760B (en) * | 2009-08-22 | 2012-11-14 | 西北师范大学 | Electrochemical detection method of hydroquinone |
| 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 |
| 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 |
| CN105764838A (en) * | 2013-11-20 | 2016-07-13 | 佛罗里达大学研究基金会有限公司 | Carbon dioxide reduction over carbon-containing materials |
| 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 |
| US10115972B2 (en) | 2009-04-30 | 2018-10-30 | University Of Florida Research Foundation, Incorporated | Single wall carbon nanotube based air cathodes |
| US10181614B2 (en) | 2010-12-17 | 2019-01-15 | University Of Florida Research Foundation, Incorporated | Hydrogen oxidation and generation over carbon films |
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2002
- 2002-04-05 CN CNB021164525A patent/CN1170006C/en not_active Expired - Fee Related
Cited By (13)
| 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 |
| US10181614B2 (en) | 2010-12-17 | 2019-01-15 | University Of Florida Research Foundation, Incorporated | 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 |
| CN102423705A (en) * | 2011-10-17 | 2012-04-25 | 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 |
| CN105764838A (en) * | 2013-11-20 | 2016-07-13 | 佛罗里达大学研究基金会有限公司 | Carbon dioxide reduction over carbon-containing materials |
| CN105764838B (en) * | 2013-11-20 | 2019-03-01 | 佛罗里达大学研究基金会有限公司 | Carbon dioxide reduction on carbonaceous material |
| US10815576B2 (en) | 2013-11-20 | 2020-10-27 | University Of Florida Research Foundation, Incorporated | 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 |
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