CN101825601A - Method for preparing high-performance Prussian blue modified electrode - Google Patents
Method for preparing high-performance Prussian blue modified electrode Download PDFInfo
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Abstract
The invention relates to a method for preparing a high-performance Prussian blue modified electrode, and aims to solve the technical problem that a biosensor constructed by combining Prussian blue with peroxidase in the field of electrochemistry affects the improvement of the performance of an electrochemical sensor and also affects the detecting performance of an electrochemical biosensor in a long-term continuous operating environment because of the restriction of the performance of the Prussian blue per se. Ionic liquid is used as a solution additive, and the electrode prepared by the method is used for electrochemical analysis. Experiment results show that the electro-deposition rate of the Prussian blue on the surface of the electrode is promoted due to the existence of the ionic liquid, so the Prussian blue modified electrode has high electrochemical performance. Taking catalysis of hydrogen peroxide for an example, compared with the Prussian blue modified electrode prepared under a condition without the ionic liquid, the Prussian blue modified electrode prepared by the method shows higher sensitivity and wider linear range to the catalysis of the hydrogen peroxide. The method has the characteristics of simpleness, high speed and easy operation. By using the electrode as a substrate, an enzyme biosensor can be prepared by further immobilizing enzyme, so the method also has potential application value in the aspect of the electrochemical biosensor.
Description
Technical field
The invention belongs to the preparing technical field of modified electrode with electric catalyticing characteristic, being particularly related to a kind of is the preparation method of the high-performance Prussian blue modified electrode of solution additive with the ionic liquid, and be used for electrochemical analysis with this electrode, and as: the detection of the concentration of hydrogen peroxide.
Background technology
The Prussian blue multinuclear transition metal prussiate that belongs to, has unique electric chromatic effect, magnetic, electrocatalysis etc., the typical case who often is used as the multi-nuclear metal prussiate represents and studies the application of such material in fields such as electrochromism, magnetic, electrochemical catalysis, electrochemical analysiss.In electrochemical field, have excellent electrochemical reversibility owing to Prussian blue, thereby be used as electron mediator widely.By with itself and enzyme further combined with making up biology sensor.For example, Prussian blue normal the combination with peroxidase makes up second generation electrochemica biological sensor, is used for H
2O
2Detection Deng the life metabolite.Yet, under long-term, continuous operating environment, Prussian blue because the restriction of self performance has influenced the raising of performance of electrochemical sensors.Therefore, the Prussian blue modified electrode that processability is good is most important for the detection performance that improves electrochemica biological sensor.
Prussian blue preparation method is a lot, as chemical method, electrodeposition process etc.Wherein, electrodeposition process is owing to have characteristics such as quick, simple, economic, controlled, and has been subjected to people's favor.Over past ten years, use the electrodeposition technology for preparing Prussian blue modified electrode to be widely studied, the normal electrode basement that adopts comprises: gold, platinum, glass carbon, carbon fiber, carbon paste electrode etc.
At present, use the electrodeposition technology for preparing high-performance Prussian blue modified electrode to mainly contain following two kinds of approach: the one, after electrode surface suitably modified, carry out Prussian blue deposition.As: to the carbon fiber electrode surface, can find that Prussian blue deposition is more effective with carbon nano tube modified; Li et al. working load the branch shape chemicals of nm of gold carry out electrode modification, then by the prepared by electrodeposition Prussian blue modified electrode, this electrode shows the applicable scope of very wide pH as a result, better electrochemical stability and the response performance bigger to hydrogen peroxide.The 2nd, in solution, add adjuvant, under the condition of source of iron and adjuvant coexistence, prepare Prussian blue modified electrode.As: surfactant is carried out Prussian blue deposition as adjuvant, also can obtain high-performance Prussian blue modified electrode.At present, multiple anionic surfactant, cationic surfactant, non-ionic surfactant have been used to improve the performance of Prussian blue modified electrode as adjuvant.Recently, Vittal andKumar especially points out with hexadecyl trimethyl ammonium bromide Prussian blue as the adjuvant electro-deposition, can obtain extraordinary performance, as the Prussian blue modified electrode for preparing has higher current-responsive, electron transfer rate and better premium properties such as stability fast.
As can be seen, use the Prussian blue method of additive preparation high-performance simpler, quick, yet used adjuvant only is the surfactant of several a few species at present.The adjuvant of developing new product variety is significant for the preparation high-performance Prussian blue modified electrode.
Summary of the invention
The present invention is in order to solve in electrochemical field with the Prussian blue biology sensor that makes up that combines with peroxidase, under long-term, continuous operating environment, because the Prussian blue restriction that is subjected to self performance, and influenced the raising of performance of electrochemical sensors, can make the affected technical matters of detection performance of electrochemica biological sensor, a kind of high-performance Prussian blue modified electrode preparation method is provided.Described Prussian blue modified electrode is to utilize electrodeposition process, prepares under ionic liquid and source of iron concurrent conditions.Preparation process is as follows:
With chlorination 1-butyl 3-methylimidazole, [Bmim] [Cl] ionic liquid is as solution additive, and its concentration is 0.0mM-0.6mM; Acid solution and 0.5mMFeCl at the 0.02M of pH=1.7 HCl+0.1M KCl
3+ 0.5mM K
3[Fe (CN)
6] in the solution of coexistence, insert pretreated naked carbon paste electrode, in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out cyclic voltammetry scan, scintigram speed is 40 circles, obtains the Prussian blue modified electrode of improvement in performance.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate and make Prussian blue modified electrode.
The invention has the beneficial effects as follows that adopting concentration is that [Bmim] [Cl] of 0.2mM is solution additive, is containing 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in 1.7 the acid solution, to be that basal electrode passes through the prepared by electrodeposition high-performance Prussian blue modified electrode with the carbon paste electrode.Because ionic liquid can effectively adsorb on the carbon paste electrode surface, thereby with the electrode surface electric chargeization, under the effect of the positive charge that electrode surface had, because electrostatic interaction has promoted ferric ion-iron cyanide ion to the facilitation to deposition.In addition, be dissolved in the solution ionic liquid since himself design feature also show the facilitation of ferric ion-iron cyanide ion deposition.The Prussian blue modified electrode for preparing with under the same electrical chemical preparation parameter condition, the Prussian blue modified electrode for preparing under the no ionic liquid existence condition compares, it is about 50% that its current-responsive has improved, and the catalysis of hydrogen peroxide is had bigger sensitivity and wideer sensing range.This method is simple, convenient, controlled, is the effective means of preparation high-performance Prussian blue modified electrode.
Description of drawings
Fig. 1 carbon paste electrode synoptic diagram.
Fig. 2 is Prussian blue electric deposition device.
Fig. 3 is at 0.2mM[Bmim] in the presence of the Cl, the Prussian blue modified electrode for preparing is to hydrogen peroxide catalyzed timing ampere figure.
Embodiment
A kind of high-performance Prussian blue modified electrode preparation method, working electrode is substrate with the carbon paste electrode, utilizes electrodeposition process to prepare under ionic liquid and source of iron concurrent conditions.Preparation process is as follows:
With chlorination 1-butyl 3-methylimidazole, [Bmim] [Cl] ionic liquid is as solution additive, and its concentration is 0.0mM-0.6mM; Acid solution and 0.5mMFeCl at the 0.02M of pH=1.7 HCl+0.1M KCl
3+ 0.5mM K
3[Fe (CN)
6] in the solution of coexistence, insert pretreated naked carbon paste electrode, in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out cyclic voltammetry scan, the scanning Lap Time is 40 circles, obtains the Prussian blue modified electrode of improvement in performance.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate and make Prussian blue modified electrode.
Wherein:
Described ion liquid variable concentrations is respectively (a) 0mM (keeping, is in order to contrast the modified electrode performance that has under the ionic liquid existence condition), (b) 0.1mM, (c) 0.2mM. (d) 0.3mM, (e) 0.4mM, (f) 0.5mM, (g) 0.6mM.
Described carbon electrode is a kind of in carbon paste electrode, the glass-carbon electrode.
Described ion liquid optium concentration is 0.2mM.
Described electrodeposition process is a cyclic voltammetry.
The preparation of described carbon paste electrode 4: with diameter is electric conductivity carbon dust and the whiteruss mixing of 0.02-0.01mm, and grinds; Carbon dust: whiteruss=5g: 2.5ml; Ground potpourri carbon paste 3 is inserted compacting in the glass tube 2, and interpolation copper rod 1 can obtain the whiteruss carbon paste electrode as lead; Before using electrode surface is polished into minute surface on pan paper.
Described electrodeposition process by Prussian blue electric deposition device with pretreated carbon electrode as working electrode, place the acid solution 7 of described ionic liquid and source of iron coexistence, with platinum filament 5 is to electrode, with Ag/AgCl or saturated KCl is contrast electrode 6, use the AUTOLAB electrochemical workstation, in-200 to 1000mV potential range, be that 100mV s-1 carries out 40 circle cyclic voltammetry scans, make the Prussian blue modified electrode of high electrochemical performance to sweep speed.
Referring to Fig. 1, the preparation of described carbon paste electrode 4: with diameter is electric conductivity carbon dust and the whiteruss mixing of 0.02-0.01mm, and grinds; Carbon dust: whiteruss=5g: 2.5ml; Ground potpourri carbon paste 3 is inserted compacting in the glass tube 2, and interpolation copper rod 1 can obtain the whiteruss carbon paste electrode as lead; Before using electrode surface is polished into minute surface on pan paper.
Referring to Fig. 2, described electrodeposition process by Prussian blue electric deposition device with pretreated naked carbon paste electrode 4 as working electrode, place the ionic liquid that contains variable concentrations, 0.5 mM FeCl
3With 0.5mMK
3[Fe (CN)
6] the pH value be in 1.7 the acid solution 7, to be to electrode with platinum filament 5, be contrast electrode 6 with Ag/AgCl (saturated KCl), use AUTOLAB (Dutch AUTOLAB company) electrochemical workstation, in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, because [Bmim]+with π-π interaction of electrode surface, and ion liquid special construction makes under the ionic liquid existence condition, obtained not having under the ionic liquid condition, had more high electrochemical performance Prussian blue modified electrode.
Above-mentioned Prussian blue modified electrode is taken out from solution, carry out three flushings, to wash the ionic liquid that is adsorbed on electrode surface and the various ions in the mother liquor off with redistilled water.Subsequently, Prussian blue modified electrode is carried out activation processing, that is, place 90 degrees centigrade thermostatic drying chamber to carry out drying half an hour at electrode.
The Prussian blue modified electrode that drying is crossed places the blank solution that contains 0.02M HCl and 0.1 M KCl, is 100mV s to sweep speed in-200 to 600mV potential range
-1Scan, obtain having the cyclic voltammetry curve of different electrochemical response signals.With the reduction peak current is references object, investigates under the preparation condition of different ionic liquid concentration the disproportionation feature of the Prussian blue modified electrode for preparing.
Embodiment 1:
Pretreated naked carbon paste electrode 4 is placed the ionic liquid that contains 0.0mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament 5, be contrast electrode 6 with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain not having the Prussian blue modified electrode for preparing under the ionic liquid condition.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02.M HCl and 0.1M KCl, is 100mV s to sweep speed in-200 to 600mV potential range
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 3.736mA/cm
2
Embodiment 2:
Pretreated naked carbon paste electrode 4 is placed the ionic liquid that contains 0.1mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament 5, be contrast electrode 6 with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain the Prussian blue modified electrode that under 0.1mM ionic liquid existence condition, prepares.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl, is 100mVs to sweep speed in-200 to 600mV potential range
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 4.328mA/cm
2
Embodiment 3:
Referring to Fig. 3, pretreated naked carbon paste electrode 4 is placed the ionic liquid that contains 0.2mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament 5, be contrast electrode 6 with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain the Prussian blue modified electrode that under 0.2mM ionic liquid existence condition, prepares.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl, is 100mV s to sweep speed in-200 to 600mV potential range
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 6.156mA/cm
2
Embodiment 4:
Pretreated naked carbon paste electrode 4 is placed the ionic liquid that contains 0.3mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament 5, be contrast electrode 6 with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain the Prussian blue modified electrode (experimental provision as shown in Figure 1) that under 0.3mM ionic liquid existence condition, prepares.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl ,-200 to 600mV's. be 100mV s to sweep speed in the gesture scope
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 5.12mA/cm
2
Embodiment 5:
Pretreated naked carbon paste electrode 4 is placed the ionic liquid that contains 0.4mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament 5, be contrast electrode 6 with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain the Prussian blue modified electrode that under 0.4mM ionic liquid existence condition, prepares.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl, is 100mVs to sweep speed in-200 to 600mV potential range
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 4.79mA/cm
2
Embodiment 6:
Pretreated naked carbon paste electrode 4 is placed the ionic liquid that contains 0.5mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament, be contrast electrode with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain the Prussian blue modified electrode that under 0.5mM ionic liquid existence condition, prepares.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl, is 100mV s to sweep speed in-200 to 600mV potential range
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 4.68mA/cm
2
Embodiment 7:
Pretreated naked carbon paste electrode is placed the ionic liquid that contains 0.6mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament, be contrast electrode with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, obtain the Prussian blue modified electrode that under 0.6mM ionic liquid existence condition, prepares.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl, is 100mV s to sweep speed in-200 to 600mV potential range
-1Scan, obtain cyclic voltammetry curve.Its reduction peak current value is: 5.14mA/cm
2
Embodiment 8: pretreated glass-carbon electrode is placed the ionic liquid that contains 0.2mM as working electrode, 0.5mM FeCl
3With 0.5mM K
3[Fe (CN)
6] the pH value be in the solution of 1.7 acid solution 7, be to electrode with platinum filament, be contrast electrode with Ag/AgCl (saturated KCl), in-200 to 1000mV potential range, be 100mV s to sweep speed
-1Carry out 40 circle cyclic voltammetry scans, its redox current-responsive is the current-responsive when preparing under no ionic liquid existence condition all.With electrode with redistilled water flushing three times after, put into thermostatic drying chamber in 90 degrees centigrade down dry 30min activate.Electrode after the activation is inserted in the blank solution of 0.02M HCl and 0.1M KCl, is 100mV s to sweep speed in-200 to 600mV potential range
-1Scan, the redox electric current that obtains cyclic voltammetry curve all descends the current-responsive of the Prussian blue modified electrode of preparation greater than no ionic liquid existence condition.
By relatively, can obtain preparation condition, that is: the best ion strength of fluid corresponding to Prussian blue modified electrode with peak response electric current.Definite through testing, the best ion strength of fluid is 0.2mM.
By embodiment 8, the suitable electrode of this method is applicable to too and uses glass-carbon electrode to be substrate as can be known, the preparation high-performance Prussian blue modified electrode.
With the best ion strength of fluid is preparation condition, and the Prussian blue modified electrode for preparing is used for electrochemical analysis.To detect hydrogen peroxide is example, and usually, the reduction potential that detects hydrogen peroxide by timing ampere method on naked carbon paste electrode is about 0.6V, and such noble potential usually can cause the oxidation that detects other materials in the solution, thereby brings interference for detection.But use Prussian blue modified electrode to detect hydrogen peroxide, detect current potential and then reduce greatly.In this experiment, in order to detect concentration of hydrogen peroxide, we will detect current potential and be made as 0v.With the Prussian blue modified electrode is working electrode, adopt three-electrode system, in the blank solution of the 0.02M of 8mL HCl and 0.1M KCl, add certain density hydrogen peroxide 10 μ L (as shown in Figure 2) second every 20-30, solution concentration is increased progressively with the concentration of 0.5mL, thereby obtain the i-t curve (shown in figure three) of Prussian blue modified electrode catalyzing hydrogen peroxide, set up the linear relationship between concentration of hydrogen peroxide and the electric current.Experimental result shows that Prussian blue modified electrode to the detection range of linearity of hydrogen peroxide is: 0.50mM-6.0mM, sensitivity is 0.98A M
-1Cm
-2Do not have the Prussian blue modified electrode for preparing under the system that ionic liquid exists with routine and the catalytic performance of hydrogen peroxide is compared (detecting the range of linearity is: 0.50mM-4.0mM, sensitivity is 0.45A M
-1Cm
-2), its sensitivity is higher, and the range of linearity of detection is wideer.
By repetition test, comparison, research, we can find that adding additive preparation high-performance Prussian blue modified electrode is simpler, convenient in solution.Yet used adjuvant only is the surfactant of several a few species at present.Using ionic liquid as adjuvant, is a kind of new trial.Ion liquid use if can reach the imagination that expection improves Prussian blue chemical property and catalytic performance, not only can be expanded the kind of adjuvant, but also a new platform has been started in the preparation that can be high-performance Prussian blue modified electrode.
Claims (6)
1. the preparation method of a high-performance Prussian blue modified electrode, it is characterized in that: this method is utilized electrodeposition process, under ionic liquid and source of iron concurrent conditions, with chlorination 1-butyl 3-methylimidazole, [Bmim] [Cl] ionic liquid is as solution additive, and its concentration is 0.0mM-0.6mM; Acid solution and 0.5mM FeCl at the 0.02M of pH=1.7 HCl+0.1M KCl
3+ 0.5mM K
3[Fe (CN)
6] in the solution of coexistence, working electrode is substrate with the carbon electrode, the Prussian blue modified electrode that makes with electrodeposition process.
2. the preparation method of a kind of high-performance Prussian blue modified electrode according to claim 1 is characterized in that: described carbon electrode is a kind of in carbon paste electrode, the glass-carbon electrode.
3. the carbon paste electrode that uses according to claim 1 is substrate, and a kind of preparation method of high-performance Prussian blue modified electrode is characterized in that: described ion liquid optium concentration is 0.2mM.
4. the preparation method of a kind of high-performance Prussian blue modified electrode according to claim 1, it is characterized in that: described electrodeposition process is a cyclic voltammetry.
5. the preparation method of a kind of high-performance Prussian blue modified electrode according to claim 1 is characterized in that: the preparation of described carbon paste electrode (4): with diameter is that electric conductivity carbon dust and the whiteruss of 0.02-0.01mm mixes, and grinds; Carbon dust: whiteruss=5g: 2.5ml; Ground potpourri carbon paste (3) is inserted compacting in the glass tube (2), and interpolation copper rod (1) can obtain the whiteruss carbon paste electrode as lead; Before using electrode surface is polished into minute surface on pan paper.
6. the preparation method of a kind of high-performance Prussian blue modified electrode according to claim 1, it is characterized in that: described electrodeposition process by Prussian blue electric deposition device with pretreated carbon electrode as working electrode, place the acid solution (7) of described ionic liquid and source of iron coexistence, with platinum filament (5) is to electrode, with Ag/AgCl or saturated KCl is contrast electrode (6), use the AUTOLAB electrochemical workstation, in-200 to 1000mV potential range, be that 100mV s-1 carries out 40 circle cyclic voltammetry scans, make the Prussian blue modified electrode of high electrochemical performance to sweep speed.
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Cited By (8)
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|---|---|---|---|---|
| WO2012113142A1 (en) * | 2011-02-23 | 2012-08-30 | 江西隆丰工贸有限责任公司 | Manufacturing method of hemoglobin modified electrode for detecting hydrogen peroxide |
| CN103073028A (en) * | 2012-12-21 | 2013-05-01 | 河南大学 | Magnetic nano-Turnbull's blue and its preparation method and use |
| CN103543187A (en) * | 2012-07-12 | 2014-01-29 | 西北师范大学 | Hydrophobic ionic liquid fixed cholesterol enzyme/Prussian blue modified electrode for detecting cholesterol |
| CN108063266A (en) * | 2017-12-14 | 2018-05-22 | 扬州大学 | A kind of preparation method of the Prussian blue similar object modified electrode of high-performance |
| CN110146563A (en) * | 2018-12-17 | 2019-08-20 | 浙江大学山东工业技术研究院 | It is a kind of based on Prussian blue no enzymuria acid sensor |
| CN111060573A (en) * | 2019-12-19 | 2020-04-24 | 衡阳师范学院 | CoFe Prussian blue analogue modified electrode and application thereof in simultaneous determination of dopamine and 5-hydroxytryptamine contents |
| KR102115968B1 (en) * | 2019-01-30 | 2020-05-27 | 재단법인대구경북과학기술원 | Method of manufacturing carbon nanofiber electrode loaded with prussian blue removal method of radioactive cesium using the same |
| CN113092566A (en) * | 2021-03-12 | 2021-07-09 | 华东师范大学 | Cellulose acetate compound and preparation method and application thereof |
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| WO2012113142A1 (en) * | 2011-02-23 | 2012-08-30 | 江西隆丰工贸有限责任公司 | Manufacturing method of hemoglobin modified electrode for detecting hydrogen peroxide |
| CN103543187A (en) * | 2012-07-12 | 2014-01-29 | 西北师范大学 | Hydrophobic ionic liquid fixed cholesterol enzyme/Prussian blue modified electrode for detecting cholesterol |
| CN103073028A (en) * | 2012-12-21 | 2013-05-01 | 河南大学 | Magnetic nano-Turnbull's blue and its preparation method and use |
| CN103073028B (en) * | 2012-12-21 | 2015-08-19 | 河南大学 | A kind of magnetic Nano Teng Shi is blue and its preparation method and application |
| CN108063266A (en) * | 2017-12-14 | 2018-05-22 | 扬州大学 | A kind of preparation method of the Prussian blue similar object modified electrode of high-performance |
| CN110146563A (en) * | 2018-12-17 | 2019-08-20 | 浙江大学山东工业技术研究院 | It is a kind of based on Prussian blue no enzymuria acid sensor |
| KR102115968B1 (en) * | 2019-01-30 | 2020-05-27 | 재단법인대구경북과학기술원 | Method of manufacturing carbon nanofiber electrode loaded with prussian blue removal method of radioactive cesium using the same |
| CN111060573A (en) * | 2019-12-19 | 2020-04-24 | 衡阳师范学院 | CoFe Prussian blue analogue modified electrode and application thereof in simultaneous determination of dopamine and 5-hydroxytryptamine contents |
| CN111060573B (en) * | 2019-12-19 | 2022-07-08 | 衡阳师范学院 | CoFe Prussian blue analogue modified electrode and application thereof in simultaneous determination of dopamine and 5-hydroxytryptamine contents |
| CN113092566A (en) * | 2021-03-12 | 2021-07-09 | 华东师范大学 | Cellulose acetate compound and preparation method and application thereof |
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