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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 PDF

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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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electrode
porphyrin
heteropolyacid
carbon electrode
modified
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CN1170006C (en
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董绍俊
申燕
刘健允
刘柏峰
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Changchun Institute of Applied Chemistry of CAS
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Changchun Institute of Applied Chemistry of CAS
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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

The preparation method of efficient catalytic oxidation-reduction porphyrin/heteropolyacid multi-layer carbon film electrode
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)

1.一种高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于，基底预修饰：选择预修饰材料为4-氨基苯甲酸浓度为1～100mM，支持电解质高氯酸锂浓度为100mM，将两者同时溶于无水乙醇或者无水乙腈溶液中，铂片作为对电极；无水乙醇或者无水乙腈溶液中以Ag/Ag+为参比电极，水溶液中以Ag/AgCl为参比电极；玻璃碳、碳纤维、或石墨电极作为修饰基底；1. A method for preparing a high-efficiency catalytic oxygen reduction porphyrin/heteropolyacid multilayer carbon electrode, characterized in that the substrate is pre-modified: the pre-modified material is selected to be 4-aminobenzoic acid with a concentration of 1-100mM, and the supporting electrolyte is high The concentration of lithium chlorate is 100mM, and the two are dissolved in absolute ethanol or anhydrous acetonitrile solution at the same time, and the platinum sheet is used as a counter electrode; Ag/Ag + is used as a reference electrode in anhydrous ethanol or anhydrous acetonitrile solution, Use Ag/AgCl as a reference electrode; glassy carbon, carbon fiber, or graphite electrodes as modified substrates; 电极制作过程如下：The electrode fabrication process is as follows: 1)在室温下把干净的碳电极浸入到上述电解质溶液中，在0～1.4V电位范围内，在10mV/s的扫速下进行循环电位扫描，冲洗，得到富含羧基官能团的单分子前体膜修饰碳电极；1) Immerse a clean carbon electrode into the above electrolyte solution at room temperature, perform cyclic potential scanning at a scanning rate of 10 mV/s in the potential range of 0 to 1.4 V, and rinse to obtain monomolecular precursors rich in carboxyl functional groups. Bulk membrane modified carbon electrodes; 2)将修饰有该前体膜的碳电极浸入到含0.5～10mM四甲基吡啶钴卟啉或四甲基吡啶铁卟啉的100mM醋酸缓冲液中pH＝3.3～3.8，在0.4～-0.4V范围内以10～100mV s-1的扫速进行循环伏安扫描；取出电极，水冲洗；2) Immerse the carbon electrode modified with the precursor film into 100mM acetate buffer solution containing 0.5-10mM tetramethylpyridine cobalt porphyrin or tetramethylpyridine iron porphyrin, pH=3.3-3.8, at 0.4-0.4 In the range of V, perform cyclic voltammetry scanning at a scanning rate of 10-100mV s -1 ; take out the electrode and rinse it with water; 3)再将2)所得电极转移到含0.5～10mM磷二钨十八酸、硅钨十二酸或者磷二钼十八酸的100mM硫酸溶液中在0.3～-0.3V范围内以10～100mVs-1的扫速进行循环伏安扫描；取出电极，冲洗；3) Transfer the electrode obtained in 2) to a 100mM sulfuric acid solution containing 0.5-10mM ditungstooctadecanoic acid, silicotungstodecanoic acid or dimolybdenum-octadecanoic acid at 10-100mVs in the range of 0.3-0.3V -1 scan rate for cyclic voltammetry scan; remove the electrode, rinse; 4)重复2)、3)两步操作，即可得到卟啉/杂多酸多层膜修饰电极。4) Repeat the two steps 2) and 3) to obtain a porphyrin/heteropolyacid multilayer modified electrode. 2.如权利要求1所述的高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于将富含羧基官能团的单分子前体膜修饰碳电极浸入到甲基吡啶钴卟啉。2. the preparation method of efficient catalytic oxygen reduction porphyrin/heteropolyacid multilayer film carbon electrode as claimed in claim 1 is characterized in that the monomolecular precursor film modification carbon electrode that is rich in carboxyl functional group is immersed in picoline cobalt porphyrin. 3.如权利要求1所述的高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于将富含羧基官能团的单分子前体膜修饰碳电极浸入到四甲基吡啶铁卟啉。3. the preparation method of efficient catalytic oxygen reduction porphyrin/heteropolyacid multilayer carbon electrode as claimed in claim 1 is characterized in that the monomolecular precursor film modification carbon electrode that is rich in carboxyl functional group is immersed in tetramethyl Pyridine iron porphyrin. 4.如权利要求1所述的高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于将2)所得电极转移到磷二钨十八的硫酸溶液中。4. the preparation method of highly efficient catalytic oxygen reduction porphyrin/heteropolyacid multilayer carbon electrode as claimed in claim 1, is characterized in that 2) gained electrode is transferred in the sulfuric acid solution of phosphorus ditungsten octadecyl. 5.如权利要求1所述的高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于将2)所得电极转移到硅钨十二酸的硫酸溶液中。5. the preparation method of highly efficient catalytic oxygen reduction porphyrin/heteropolyacid multilayer carbon electrode as claimed in claim 1, is characterized in that 2) gained electrode is transferred in the sulfuric acid solution of silicon tungsten dodecanoic acid. 6.如权利要求1所述的高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于将2)所得电极转移到磷二钼十八硫酸溶液中。6. the preparation method of highly efficient catalytic oxygen reduction porphyrin/heteropolyacid multilayer carbon electrode as claimed in claim 1, is characterized in that 2) gained electrode is transferred in the phosphorus dimolybdenum octadecadecanoic acid solution. 7.如权利要求1所述的高效催化氧还原卟啉/杂多酸多层膜碳电极的制备方法，其特征在于选择四甲基吡啶钴卟啉或四甲基吡啶铁卟啉与磷二钨十八、硅钨十二或磷二钼十八进行多层修饰。7. the preparation method of efficient catalytic oxygen reduction porphyrin/heteropolyacid multilayer carbon electrode as claimed in claim 1 is characterized in that selecting tetramethylpyridine cobalt porphyrin or tetramethylpyridine iron porphyrin and phosphorus di Tungsten eighteen, silicon tungsten twelve or phosphorus dimolybdenum eighteen for multi-layer modification.
CNB021164525A 2002-04-05 2002-04-05 Preparation method of porphyrin/heteropolyacid multilayer carbon electrode for catalytic oxygen reduction Expired - Fee Related CN1170006C (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN100380115C (en) * 2005-01-10 2008-04-09 厦门大学 A kind of polymer membrane 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 on carbonaceous 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
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Cited By (13)

* Cited by examiner, † Cited by third party
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CN100380115C (en) * 2005-01-10 2008-04-09 厦门大学 A kind of polymer membrane 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 on carbonaceous 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 materials
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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