CN100447562C - Methanol electro-oxidizing-catalyzing electrode, preparing process and application thereof - Google Patents
Methanol electro-oxidizing-catalyzing electrode, preparing process and application thereof Download PDFInfo
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- CN100447562C CN100447562C CNB2005100002883A CN200510000288A CN100447562C CN 100447562 C CN100447562 C CN 100447562C CN B2005100002883 A CNB2005100002883 A CN B2005100002883A CN 200510000288 A CN200510000288 A CN 200510000288A CN 100447562 C CN100447562 C CN 100447562C
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Abstract
The present invention discloses a methanol electric oxidizing catalysis electrode, a preparing method thereof and the application thereof, which relates to a metalized film modified electrode. The present invention provides a methanol electric oxidizing catalysis electrode and a preparing method thereof, and the methanol electric oxidizing catalysis electrode is used as an electrochemical sensor for catalyzing the electric oxidation of methanol. The methanol electric oxidizing catalysis electrode is a metalized film modified electrode of poly 2, 5-dimethoxyaniline as a polyaniline derivative, which has strong electron donating groups; the methanol electric oxidizing catalysis electrode comprises an inert electrode substrate, an electrically conductive polymer film and a catalyst, and the attachment amount of a polymer on the surface of the substrate electrode ranges from 0.3 to 1.0 mg. cm<-2>. The preparing method comprises the steps that hydrochloric acid doped PDMAn is dissolved in N, N-dimethylformamide or tetrahydrofuran so as to prepare a solution of 1.0 to 10.0 mg/mL; the surface of an electrode is coated with a polymer solution, and the electrode is dried; the coating number of times is changed to adjust the attachment amount of the polymer on the electrode surface; the electrode is placed in H2PtCl6 or an HCl solution of H2PtCl6, potential controlled circulating scanning or unidirectional scanning is carried out, and the number of times is changed; consequently, modified electrodes with different platinum deposition amounts can be obtained.
Description
Technical field
The present invention relates to a kind of metalized film modified electrode, especially a kind of polyaniline derivative with strong donor residues gathers 2,5-dimethoxyaniline metalized film modified electrode and preparation method, and with its electrochemical sensor as the catalysis methanol electrooxidation.
Background technology
Industrial chemicals methyl alcohol is a kind of harmful toxic matter, when people's body disposable excess intake, vomiting, stomachache, vision disorder, serious toxicity symptom such as short of breath can occur, the people is lost consciousness and dead.By the fake wine that the industrial spirit that contains methyl alcohol is made, make a lot of consumers blind or lost life.Measuring methanol content at present mainly is to adopt vapor-phase chromatography, spectrophotometric method and electro-catalysis method.
Depositing the electrochemical catalyst that platinum (Pt) preparation is applicable to methanol oxidation on carrier, is one of important research direction of methyl alcohol detecting sensor preparation.
Pt is considered to the higher a kind of noble metal of catalytic activity, and the Pt series catalysts is a kind of effective methanol oxidation catalyst system.Methanol oxidation is a kind of complex process of multistep dehydrogenation, and wherein oxidizing process can produce some toxicity intermediate (CO
AbsorptionOr COH
Absorption) be adsorbed in electrode surface, occupy the effective active position of Pt catalysis, make electrode lose activity.Only in electro-oxidation reaction, generate oxide on surface OH in a large number
Absorption, methyl alcohol is completely oxidized to CO
2, could improve the efficient of methanol oxidation process.Therefore when development and the agent of exploitation methanol electro-oxidizing-catalyzing, consider to change the crystalline texture of catalyzer, increase adsorbance, reduce the adsorbance of toxicity intermediate methyl alcohol and active intermediate product thereof.People have decisive influence [list of references: Sun S G, ChenA C, Huang T S etal, Journal ofElectroanal Chem, 1992,340:213-226] by a large amount of surface structures of discovering Pt particulate on the electrode to its activity.The subject matter that the Pt series catalysts exists is exactly to adsorb the toxicity intermediate easily, and stability in use is poor.Fig. 1 be cyclic voltammetry curve in the sulfuric acid medium that contains 0.72mol/L methyl alcohol of the Pt electrode of deposition Pt particulate (in Fig. 1, horizontal ordinate is current potential/voltage, i.e. E/V vs SCE, ordinate is oxidation peak current density j/mAcm
-2), along with increasing of the circulation number of turns, oxidation peak current descends gradually, and declines by a big margin.This is because methanol oxidation process toxic intermediate occupies the active sites of Pt crystal, makes the catalytic performance of electrode descend.
In the development research of precious metals pt series catalysts, except adopting thermometal or three metal alloys, the research of precious metal catalyst agent carrier also is an important directions.What be commonly used for catalyst support at present has material with carbon element, a polymkeric substance etc., adopts sol-gel process to prepare acticarbon as [list of references: Liu Changpeng, Yang Hui etc., SCI, 2002,23 (7): 1367-1370] such as Liu Changpeng and carries Pt-TiO
2Catalyzer is applied to fuel cell; Yang Hui etc. [Yang Hui, Li Changzhi, Acta PhySico-Chimica Sinica, 1997,13 (6): 542-547] adopt poly-thionine to be modified on the glass-carbon electrode as the carrier of Pt particle deposition, are applied to the electrooxidation research of methyl alcohol.Polymer support is owing to have tridimensional network, be difficult for running off, stable performance is a kind of good catalyst support, wherein the oxidation-reduction type polymkeric substance has electrocatalysis characteristic in its active potential range, can show some special performances during as the precious metal catalyst agent carrier.
Electronic conductive polymer polyaniline and derivant thereof are the redox polymerses of a quasi-representative, three kinds of states of its oxidation-reduction process experience: go back ortho states (L), semi-oxidation state (E) and complete oxidation attitude (P) fully [referring to document: Tawde S etal, Synthetic Metals, 2002,125:401-413], it goes back ortho states/semi-oxidation state fully, and to change on (L/E) and semi-oxidation state/complete oxidation attitude (E/P) transformation current potential and the polymer ring substituting group kind relevant with PH values.When having the donor residues replacement on the polyaniline compound electronic conductive polymer phenyl ring, help improving ring and go up cloud density, reduce the electronic transition energy level difference, make the oxidation peak current potential bear and move, improve conductivity.Because methyl alcohol has typical Langmuir adsorption phenomena [list of references: Rajendra Prasad K on polyaniline film, Munichandraiah N.Journal of Powder Sources, 2002,103:300-304], be unfavorable for the detection of low concentration methyl alcohol, the electronics selfing throw-over rate between strand increased for the introducing of electron substituent group, the absorption of methyl alcohol on polymkeric substance is not obvious, can be diffused into the Pt surface quickly and carry out oxidation, catalytic efficiency is improved.
But tool gives the polymerization oxidation current potential of electron substituent group aniline monomer lower, when adopting chemical oxidising polymerisation, be in and cause the polymkeric substance peroxidating in the strong oxidizing property polymerisation medium easily, and if free oxygen changes into the quinoid structure, just be difficult to carry out coupling with active growing chain, cause strand to increase difficulty, molecular weight of product is low, so the selection of polymerizing condition, mode seems extremely important.
Dissolving processability and bad mechanical strength are the key factors that the restriction polyaniline is used.On phenyl ring, introduce substituting group and can reduce intermolecular interaction, improved the dissolving processability of polymkeric substance.
The conductive capability of conjugated type polymkeric substance derives from macromolecular chain and forms the big π key of conjugation system, forms polaron during protonic acid doping as charge carrier, and conductive capability and conjugated degree and doping level are closely bound up.Give electronic effect when the ring substituents tool, can improve the cloud density of aromatic rings on the strand, help improving electric conductivity; Substituent steric effect then makes conjugate planes be distorted, and reduces conjugated degree, has sacrificed the electric conductivity of polymkeric substance.
Therefore how to select substituting group, do not sacrifice electric conductivity when the dissolving processability is improved, just become the polyaniline compound electronic conductive polymer and obtain key technologies for application at aspects such as electrochemical sensors.
Summary of the invention
Purpose of the present invention aims to provide a kind of methanol electro-oxidizing-catalyzing electrode and preparation method, and said methanol electro-oxidizing-catalyzing electrode is the polyaniline derivative of band symmetry strong donor residues-poly--2,5-dimethoxyaniline metalized film modified electrode.
Another object of the present invention is to methanol electro-oxidizing-catalyzing electrode, promptly the polyaniline derivative with strong donor residues gathers-2, and 5-dimethoxyaniline metalized film modified electrode is as the electrochemical sensor of catalysis methanol electrooxidation.With the polyaniline derivative of strong donor residues as sensor in the methanol electro-oxidizing process, have better catalytic performance, detection sensitivity, electrochemical stability.
The polyaniline derivative of the strong donor residues of the said band of the present invention gathers 2, and 5-dimethoxyaniline metalized film modified electrode comprises inert electrode matrix, conductive polymer membrane and catalyzer, and the adhesion amount of base electrode surface aggregate thing is 0.3～1.0mgcm
-2
The said inert electrode matrix of the present invention is platinum disc substrate, golden disk electrode matrix or glass carbon disk electrode matrix.
The said conductive polymer membrane of the present invention gathers-2,5-dimethoxyaniline (PDMAn) for the doping attitude.
The said catalyzer of the present invention is Pt, the Pt-Ru alloy particle that is deposited on polymer film surface, and deposition is 0.1～0.5mg/cm
2
The polyaniline derivative of the strong donor residues of the said band of the present invention gathers 2, and the preparation method of 5-dimethoxyaniline metalized film modified electrode is:
1) PDMAn with doped hydrochloride is dissolved in N, in dinethylformamide (DMF) or the tetrahydrofuran (THF), be made into the solution of 1.0～10.0mg/mL, get polymer solution and be coated on electrode surface, promptly get polymer film modified electrode after the oven dry, apply number of times adjustment electrode surface polymkeric substance adhesion amount by changing, adhesion amount is controlled at 0.3～1.0mgcm
-2
2) above-mentioned polymer film modified electrode is placed 0.5～2.0mg/mL H
2PtCl
6Or k
2PtCl
61.0mol/LHCl solution in, adopt control current potential scan round or simple scanning, change scanning times, can obtain the modified electrode of different platinum depositions.
The polyaniline derivative of the strong donor residues of the said band of the present invention gathers-2, and 5-dimethoxyaniline metalized film modified electrode is as the electrochemical sensor of catalysis methanol electrooxidation.
Polyaniline derivative with strong donor residues gathers-2, and 5-dimethoxyaniline preparation method's concrete steps are:
In reaction vessel, add the 100mL deionized water, add 1.5 * 10
-3～10 * 10
-3The mol lauryl sodium sulfate is as emulsifying agent, continues to stir, and dissolving is treated fully in heat temperature raising to 55～90 ℃, under the nitrogen protection, drips 10～30ml 2, the 5-dimethoxyaniline (DMAn, and xylene solution CP) (preparation in advance, 0.2mol/L); Again with 2.25 * 10
-4～7.5 * 10
-4Mol/L potassium persulfate (KPS) or ammonium persulfate (APS) are dissolved in the 30mL water, as initiating agent, are added dropwise to reaction system, continue reaction 2～6h; Stop heating, change reactor into distilling apparatus, steam dimethylbenzene, or add 36% hydrochloric acid, or adding ethanol makes emulsion breaking, suction filtration, to the filtrate non-foam, continuation is washed to filtrate colourless with ethanol, 60 ℃ of oven dry of vacuum with deionized water wash, filter cake gathers 2,5-dimethoxyaniline PDMAn (ud) for the product eigenstate; Each raw material is formed in the polymerization system: [SDS]=1～6.5 * 10
-2Mol/L, [DMAn]=0.013～0.04mol/L, [KPS] or [APS]=1.5～5 * 10
-3Mol/L.
Poly-2, the 5-dimethoxyaniline has two strong electron donating groups, and electronic effect is greater than steric effect, and (above-mentioned synthetic poly--2, the conductivity of 5-dimethoxyaniline is about 1S.cm therefore to have obtained higher electric conductivity on the basis of improving solubleness
-1, suitable with the conductance of the polyaniline of bibliographical information), have using value preferably.
Methoxyl is strong donor residues, so 2, oxidation takes place in 5-dimethoxyaniline easily in the oxidisability polymerisation medium, adopt common chemical oxidising polymerisation, be that monomer and ratio of initiator are 1: 1, make monomer and polymer chain generation peroxidating easily, and have only when polymer molecular chain is in semi-oxidation state its electrochemical activity best.For fear of over oxidation, the present invention adopts emulsion polymerization synthetic.The emulsion polymerization place is the latex bundle, and the radical cation with chaininitiation diffuses into emulsion particle gradually, makes emulsion particle energy stable existence and peroxidating can not take place, and when having protected the growing chain activity, also can make product have higher molecular weight.
The present invention modifies synthetic PDMAn in electrode surface, as the carrier of methanol electro-oxidizing-catalyzing agent, can be used for detecting the electrochemical sensor of methyl alcohol in waste water or the fake wine or is applied to catalyst film electrode in the direct alcohol fuel battery.This invention has following advantage: (1) two PDMAn that methoxyl replaces, improve the dissolving processability of polyaniline greatly, and owing to the substituent electronic effect of giving, influence little to electric conductivity.(2) the L/E oxidation peak current potential of PDMAn is positioned at 0.18V, is lower than H
2PtCl
6Begin to reduce the current potential that forms the Pt particulate, can effectively change the electronic structure of Pt particulate.For powder Pt, the strength ratio of (111) and (200) crystal face diffracted ray is 100: 53; Be deposited on PDMAn (ud) matrix, the strength ratio of Pt (111) and (200) crystal face diffracted ray is 100: 96; The ratio that is deposited on PDMAn (HCl) matrix is 100: 83 (Fig. 2); Therefore as seen (200) crystal face character of deposition Pt has obtained reinforcement on PDMAn (ud) matrix, as PDMAn during as electrode modified material, can effectively improve the anti-CO poisoning capability of platinum catalyst.(3) PDMAn can improve electrode catalyst efficient after modifying, and reduces the methanol oxidation current potential; Fig. 3 has compared the Pt electrode and the cyclic voltammetry curve of PDMAn (HCl) electrode in variable concentrations methyl alcohol of deposition Pt particulate, methyl alcohol is just being swept oxidation peak current potential (0.62V) and is being lower than Pt electrode (0.65V) on PDMAn, and after PDMAn modified, oxidation peak current improved response sensitivity with methanol concentration and is better than the Pt electrode.(4) adsorptive power of the last methyl alcohol of PDMAn is little, can effectively improve detection sensitivity.Do not deposit on the PDMAn modified electrode of Pt particulate and in low concentration methyl alcohol, occur obvious methanol oxidation peak yet, and peak current do not increase with the circulation number of turns and reduce, have catalytic activity (Fig. 4) preferably.Comparative study shows, the methanol solution of low concentration adsorption phenomena occurs on the polyaniline film modified electrode, the disproportionation peak current increases with the circulation number of turns and reduces, oxidization of methanol reaction [list of references: Rajendra Prasad K does not take place, Munichandraiah N.Journal of Powder Sources, 2002,103:300-304], this is the electronic effect of giving owing to methoxyl on the PDMAn ring, have lower L/E and change current potential, the electronics selfing throw-over rate between strand that makes increases, and the absorption of methyl alcohol on polymkeric substance is not obvious, can comparatively fast be diffused into the Pt surface and carry out oxidation.(5) the synthetic PDMAn of emulsion polymerization has avoided general in the document and has adopted problems such as polymkeric substance over oxidation that electrochemical polymerization causes, crosslinked, degraded, and can improve the molecular weight of polymerizate, obtains the good semi-oxidation state polymkeric substance of electrochemical activity.(6) PDMAn has good dissolving processability, obtains the polymer film of certain electric conductivity and thickness easily, and the catalytic performance of modified electrode and stability are all better.(7) with the carrier of conducting polymer as the Pt particle deposition, the space network of polymkeric substance provides three dimensions for the deposition of Pt particulate, under the same deposition amount, has improved the specific surface of Pt particulate greatly.(8) drop-coating prepares polymer film modified electrode, can a plurality of modified electrodes of disposable preparation, not only technology is simple, and carry out when helping detecting performance relatively, debugging.
Description of drawings
Fig. 1 is the CV figure of Pt electrode in containing the 0.72mol/L methanol solution of deposition Pt particulate.In Fig. 1, sweep velocity is 50mV/s.Horizontal ordinate is E/V vs SCE, and ordinate is j/mAcm
-2
Fig. 2 is the metallic electrode XRD spectrum of PDMAn base Pt microparticulate.In Fig. 2, horizontal ordinate is angle of diffraction 2 θ, and ordinate is diffracted intensity CPS, and a is PDMAn (ud), and b is PDMAn (HCl).
Fig. 3 is the cyclic voltammogram of variable concentrations methanol electro-oxidizing on metallized Pt of Pt and the film modified electrode of PDMAn.In Fig. 3, horizontal ordinate is E/V vs SCE, and ordinate is j/mAcm
-2, the concentration of methyl alcohol (mol/L): a=0, b=0.25, c=0.49, d=0.72.
Fig. 4 is that the PDMAn of Ptization (HCl) membrane electrode is not containing 3.0mol.L
-1Cyclic voltammogram in the acid electrolyte of methyl alcohol.In Fig. 4, horizontal ordinate is E/V vs SCE, and ordinate is j/mAcm
-2, sweep velocity: 0.5V/min, the scanning number of turns: 16 circles.
Embodiment
Embodiment 1:
PDMAn (HCl) is dissolved among the DMF, and being made into concentration is the DMF solution of 3.0mg/mL, with miniature vortex mixed instrument hydrotropy; Get a certain amount of polymer solution and be coated on the platinum disk electrode surface, place oven dry 15min in the infrared rapid draing case, promptly get polymer film modified electrode, the adhesion amount of electrode surface polymkeric substance is 0.3mgcm
-2
In single compartment electrolytic cell, as working electrode, the platinized platinum electrode is an auxiliary electrode with polymer film modified electrode, and saturated calomel electrode is a contrast electrode.Experiment is carried out on CHI660 galvanochemistry comprehensive tester, and its attached computer software can supply collection of experiment data and processing.Above-mentioned PDMAn (HCl) polymer film modified electrode is placed 1.0mg/mLH
2PtCl
61.0mol/LHCl solution in, in-0.3～0V scope, carry out current potential scan round (v=5mV/s), scan round 10 circle, obtaining the Pt deposition is 0.15mg/cm
2The metallization modified electrode.
The film modified electrode of the metallized polymeric that obtains is as working electrode, and the platinized platinum electrode is as auxiliary electrode, and saturated calomel electrode is as contrast electrode, and in single compartment electrolytic cell, potentiostat is controlled current potential, as the methyl alcohol detecting sensor.Down together.
Polyaniline derivative with strong donor residues gathers 2, and the 5-dimethoxyaniline can be prepared as follows:
In there-necked flask, add the 100mL deionized water, add lauryl sodium sulfate (SDS) 5 * 10
-3Mol continues to stir, and treats dissolving fully, and slowly dripping 20mL concentration is 2 of 0.2mol/L, and (DMAn, xylene solution CP) is under the nitrogen protection, when being warming up to 85 ℃, again with 5.0 * 10 for the 5-dimethoxyaniline
-4Mol potassium persulfate (KPS) is dissolved in the 30mL aqueous solution, stirs down slowly to add reaction system with tap funnel, continues reaction 4.0h, stop heating, change reactor into distilling apparatus, steam dimethylbenzene, make emulsion breaking, suction filtration uses the deionized water cyclic washing to the filtrate non-foam.Wash to filtrate with ethanol more colourless, 60 ℃ of oven dry of vacuum, pitchy eigenstate polymer P DMAn (ud).Above-mentioned product is placed 18% hydrochloric acid solution, stirs, be heated to boiling after, continue to stir 48h, suction filtration, with deionized water, methyl alcohol cyclic washing to neutral, purple hydrochloric acid doped P DMAn (HCl).
Embodiment 2:
With PDMAn (HClO
4) be dissolved among the DMF, with miniature vortex mixed instrument hydrotropy, concentration is 5.0mg/mL; Get a certain amount of polymer solution and be coated on the platinum disk electrode surface, place oven dry 15min in the infrared rapid draing case, promptly get polymer film modified electrode, the adhesion amount of electrode surface polymkeric substance is 0.6mgcm
-2
In single compartment electrolytic cell, as working electrode, the platinized platinum electrode is an auxiliary electrode with polymer film modified electrode, and saturated calomel electrode is a contrast electrode.Experiment is carried out on CHI660 galvanochemistry comprehensive tester, and its attached computer software can supply collection of experiment data and processing.With above-mentioned PDMAn (HClO
4) polymer film modified electrode places 1.0mg/mL H
2PtCl
61.0mol/LHCl solution in, in-0.3～0V scope, carry out current potential scan round (v=5mV/s), scan round 15 circle, obtaining the Pt deposition is 0.25mg/cm
2The metallization modified electrode.
Embodiment 3:
PDMAn (TSA) is dissolved among the DMF, and with miniature vortex mixed instrument hydrotropy, concentration is 13.0mg/mL; Get a certain amount of polymer solution and be coated on the platinum disk electrode surface, place oven dry 15min in the infrared rapid draing case, promptly get polymer film modified electrode, the adhesion amount of electrode surface polymkeric substance is 0.8mgcm
-2
In single compartment electrolytic cell, as working electrode, the platinized platinum electrode is an auxiliary electrode with polymer film modified electrode, and saturated calomel electrode is a contrast electrode.Experiment is carried out on CHI660 galvanochemistry comprehensive tester, and its attached computer software can supply collection of experiment data and processing.Above-mentioned PDMAn (TSA) polymer film modified electrode is placed 1.0mg/mL H
2PtCl
61.0mol/LHCl solution in, begin to carry out the linear control of negative sense electric potential scanning to-0.4V (v=1mV/s) from 0V, repeats 3 times, acquisition Pt deposition is 0.1mg/cm
2The metallization modified electrode.
Claims (2)
1, a kind of methanol electro-oxidizing-catalyzing electrode, it is characterized in that said methanol electro-oxidizing-catalyzing electrode is the polyaniline derivative poly-2 with strong donor residues, 5-dimethoxyaniline metalized film modified electrode, comprise inert electrode matrix, conductive polymer membrane and catalyzer, the adhesion amount of base electrode surface aggregate thing is 0.3～1.0mgcm
-2Described conductive polymer membrane gathers-2, the 5-dimethoxyaniline for the doping attitude; Described catalyzer is Pt, the Pt-Ru alloy particle that is deposited on polymer film surface, and deposition is: 0.1mg/cm
2≤ deposition＜0.5mg/cm
2
2, a kind of methanol electro-oxidizing-catalyzing electrode as claimed in claim 1 is characterized in that said inert electrode matrix is golden disk electrode matrix or glass carbon disk electrode matrix.
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| CN103063724B (en) * | 2012-12-13 | 2014-12-10 | 浙江大学 | Solid carbonate ion electrode based on conductive polyaniline and preparing method thereof |
| CN104313666B (en) * | 2014-10-14 | 2017-07-28 | 江苏科技大学 | A kind of poly- aC and polyaniline duplicature and preparation method and application |
| CN107814433B (en) * | 2017-11-01 | 2020-09-08 | 陕西科技大学 | Polymer membrane modified electrode for heavy metal wastewater electrolysis treatment and preparation method thereof |
Citations (1)
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|---|---|---|---|---|
| US5856036A (en) * | 1997-03-11 | 1999-01-05 | Illinois Institute Of Technology | Single phase ternary Pt-Ru-Os catalysts for direct oxidation fuel cells |
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|---|---|---|---|---|
| US5856036A (en) * | 1997-03-11 | 1999-01-05 | Illinois Institute Of Technology | Single phase ternary Pt-Ru-Os catalysts for direct oxidation fuel cells |
Non-Patent Citations (6)
| Title |
|---|
| 2，5-二甲氧基苯胺的乳液聚合及聚合物结构表征. 戴李宗，许一婷，邹友思，吴辉煌.应用化学，第18卷第4期. 2001 |
| 2，5-二甲氧基苯胺的乳液聚合及聚合物结构表征. 戴李宗，许一婷，邹友思，吴辉煌.应用化学，第18卷第4期. 2001 * |
| Experimental studyofplatinizedpoly-2,5-dimethoxyanilineelectrodes. Dai Lizong, Jean-Yves Gal, Huihuang Wu.Chimie / Chemistry,Vol.第4卷 . 2001 |
| Experimental studyofplatinizedpoly-2,5-dimethoxyanilineelectrodes. Dai Lizong, Jean-Yves Gal, Huihuang Wu.Chimie / Chemistry,Vol.第4卷 . 2001 * |
| 铂微粒修饰聚2，5-二甲氧基苯胺电极对甲醇的电催化作用. 万本强，吴婉群.高等学校化学学报，第16卷第4期. 1995 |
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