CN103103572A - Preparation method and application of palladium nanomaterial used as non-enzymatic glucose sensor - Google Patents
Preparation method and application of palladium nanomaterial used as non-enzymatic glucose sensor Download PDFInfo
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- CN103103572A CN103103572A CN2012105085952A CN201210508595A CN103103572A CN 103103572 A CN103103572 A CN 103103572A CN 2012105085952 A CN2012105085952 A CN 2012105085952A CN 201210508595 A CN201210508595 A CN 201210508595A CN 103103572 A CN103103572 A CN 103103572A
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Abstract
The invention relates to a preparation method and an application of a palladium nanomaterial used as a non-enzymatic glucose sensor. The technical scheme of the invention comprises the following steps of: polishing an electrode with 0.05 micron of alumina powder, washing with deionized water, and then sequentially performing ultrasonic washing by 2mol/L of NaOH, ethanol and 2mol/L of HCl and secondary water; dropping 5ml of PS globule aqueous liquor on the glassy carbon electrode of a substrate, placing away from light at room temperature, and then placing in a vacuum oven to dry at 70 DEG C to obtain a PS mould; placing the glassy carbon electrode of the substrate in PdCL2 liquor, depositing 0.03 Coulomb of Pd particles in i-t at -0.3V, slightly swinging and then, thoroughly washing with secondary water and blowing with nitrogen to obtain the palladium nanomaterial. The deficiency of the small active area is overcome. High glucose oxidization current is obtained by improving the active area of the electrode, while electrocatalytic oxidation current of concomitant interferent is not changed to a great extent, thus, the sensitivity and selectivity of analysis of glucose are improved, and meanwhile, the influence of the interferent is further eliminated.
Description
Technical field
The invention belongs to the Electrochemical Detection analysis technical field, relate to the nanometer Pd material preparation method and the application that can be used as non-enzymatic glucose sensor.
Background technology
Although the research history of enzyme-free glucose sensor is also shorter, but believe the further in-depth along with research, the particularly participation of nano-porous materials and high molecular polymer, the development of enzyme-free glucose sensor will have wider development space, make it that higher sensitivity, better selectivity and more preferably tolerance range be arranged.
Before the present invention, directly prepare nanoparticle without the enzyme nano material, the impact of the material of other that still exist such as xitix (AA), uric acid (UA), DOPA amino acid (AP).on electrode, the catalytic oxidation mechanism of glucose and its mutual interference thing is different, the catalytic oxidation process of glucose is controlled by electrode kinetics on electrode, its electrocatalytic oxidation galvanic current is directly proportional to the electrode activity surface-area, and the interfering substance that coexists with it (AA, UA, AP) electrochemical reaction rates is very fast, its electrochemistry oxygen galvanic current is controlled by the diffusion of reactant in solution, therefore their electrocatalytic oxidation galvanic current can't become large with the increase of the active area of electrode, but relevant with the apparent area of electrode, thereby produce the little defective of active area.In addition, because the electrochemical reaction rates of interfering substance is very fast, be the i-t detection method and usually check the method for glucose concn, so just must cause the accurately defective of measure glucose concentration.
Summary of the invention
The object of the invention is to overcome defects, development can be used as nanometer Pd material and preparation and the application of non-enzymatic glucose sensor.
Technical scheme of the present invention is:
Can be used as the preparation method of the nanometer Pd material of non-enzymatic glucose sensor, its major technique step is:
(1) pre-treatment of matrix glass-carbon electrode: with the aluminum oxide powder polishing of electrode with 0.05 μ m, use deionized water rinsing, more successively through 2mol/LNaOH, ethanol, 2mol/L HCl and intermediate water supersound washing;
(2) preparation of PS template: drip the PS bead aqueous solution that is coated with 5 microlitres on the matrix glass-carbon electrode that step (1) is processed, under room temperature, lucifuge is placed, then puts into oven dry under 70 ℃ of vacuum drying ovens;
(3) preparation of nanometer Pd material: the matrix glass-carbon electrode that step (2) is obtained is placed in acid PdCl2 solution, under-0.3V, i-t deposits the Pd particle of 0.03 coulomb, jiggle, then rinse well to dry up with nitrogen with intermediate water and namely obtain nanometer Pd material.
Another technical scheme of the present invention is:
Described nanometer Pd material is as the application of non-enzymatic glucose sensor, and its technical characteristics is that above-mentioned nanometer Pd material can be used as the test that the enzyme-free glucose amperometric biosensor is directly used in glucose concn.
Advantage of the present invention and effect are to obtain high glucose oxidase electric current by the active area that improves electrode, and the catalytic oxidation curent change of the chaff interference that it coexists is little, so can this improve sensitivity and selectivity to glucose analysis, can eliminate the impact of chaff interference again simultaneously.The present invention's modified electrode under alkaline environment has very high catalytic activity to glucose oxidase, thereby can be used for building high-sensitive glucose sensor.Test by condition optimizing, having obtained highly sensitive and highly selective analyzes the optimization experiment condition of glucose and is: drip and be coated with 5 μ L 1%PS, the detection current potential is 0.0V (vs.SCE), under this optimization experiment condition, modified electrode has good Anti-Jamming to UA, AP and AA, its electrochemical response is good linear relationship to glucose concn, and linearity range is 1.0-57.3mM.
Description of drawings
The SEM figure of the glass-carbon electrode that Fig. 1---PS template covers.
Fig. 2---wash away after the PS template the only SEM of the glass-carbon electrode of surplus Pd nanoparticle figure.
Fig. 3---Pd nano material by PS template preparation respectively at 0.1MNaOH without the cyclic voltammogram in glucose (c) and 1mM glucose (d), sweeping speed is 0.1V s
-1(little figure is the enlarged view of naked glass carbon CV curve, and black line a is without glucose, and red line b is for adding 1mM glucose).
Fig. 4---Pd nano material adds the i-t curve of a certain amount of glucose solution to the 0.1M NaOH under 0V.
Fig. 5---add the schematic diagram data of quantitative criterion glucose solution in containing the sample of different blood sugar concentrations.
aStandard specimen adds eight times.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment 1:
(1) pre-treatment of matrix glass-carbon electrode: with the aluminum oxide powder polishing of 0.05 μ m, the electrode of own polishing first rinses out dirt with deionized water, more successively through 2mol/L sodium hydroxide, analytical pure level ethanol, 2mol/L hydrochloric acid and intermediate water supersound washing;
(2) preparation of PS template: through dripping the PS bead aqueous solution that is coated with 5 μ L (ultrasonic evenly) on the glass-carbon electrode of pre-treatment, under room temperature, lucifuge was placed 24 hours, then put under 70 ℃ of vacuum drying ovens baking one hour; PS pellet free assembling in this process through forming the large-scale PS template of the clearly demarcated network structure of hole layer by layer on pretreated glass-carbon electrode surface, is conducive to the electrochemical deposition of the palladium particle in the 3rd step.
(3) preparation of nanometer Pd material: the electrode that will deposit the PS film is placed in acid 8mmol/L palladium chloride solution, i-t deposition 3 * 10 under-0.3V
-2The Pd particle of C.Pd ion in this Process liquor is reduced, and forms the Pd nanoparticle.The glass-carbon electrode that has adsorbed the Pd particle is put into tetrahydrofuran (THF), jiggle several under, then rinse well with nitrogen with intermediate water and dry up the Pd particle modified glassy carbon electrode that namely obtains good dispersity.
The preparation method is simple for polystyrene (PS) bead, the bead even particle size distribution, stability is preferably arranged in the aqueous solution, be soluble in organic solvent, and therefore method that can be by self-assembly prepares three-dimensional anti-phase multilayer film through being often used as mould material in the orderly arrangement of substrate surface stratiform.The gained multilayer film has the staggered pore passage structure that connects and the specific surface area of super large, and the carrier that can be used as catalytic substrate or biomolecules is used for bio-sensing.
At first, the carrier electrode for different steps in experiment is the sign that glass-carbon electrode has carried out pattern.As shown in Figure 1, PS bead size of particles homogeneous is uniformly dispersed, and marshalling has illustrated that the present invention adopts the PS template that certain scientific basis is arranged, and the good a certain amount of Pd nanoparticle of deposition and with the surface topography after the PS template removal as shown in Figure 2.After wash-out PS, the more direct galvanic deposit of Pd dispersion of particles is compared better, and the Pd nanoparticle forms reticulated structure, has greatly improved the surface-area that compares of Pd nano material, for catalytic oxidation glucose provides very large true area.
As shown in Figure 3, at first studied the electrochemical behavior of naked glass-carbon electrode.Naked glass-carbon electrode is carried out electro-chemical test in basic solution, studied the cyclic voltammogram (little figure ab curve) of electrode in adding glucose and not adding the liquid of the pure end of glucose.Can know from little figure and find out, both cyclic voltammograms are almost identical, there is no obvious redox peak.Then studied the Pd particle modified glassy carbon electrode made by the PS template in the basic solution to the electro catalytic activity of glucose.In liquid, the cyclic voltammogram of Pd (PS)-GC has not shown the feature of Pd electrode at the bottom of adding the NaOH of glucose, under-0.32V, a reduction peak is arranged.And after adding glucose, new cyclic voltammogram has shown the electrochemical behavior of glucose oxidase complexity.In the process that current potential is just being swept, an anodic oxidation peak has appearred in-0.24V place.This oxidation peak is the new palladium avtive spot of oxidation generation by CO, therefore the glucose generation direct oxidation in solution, but along with current potential continue shuffle, reaction current descends on the contrary, this explanation palladium catalyst surface formation palladium oxide, the formation of this oxide compound can reduce the avtive spot on palladium surface equally with accumulation, suppresses the direct oxidation of glucose, and glucose direct oxidation electric current is descended.Show in figure, a reduction current peak occurs in the negative process of sweeping of current potential.The reduction (cd relatively) of the palladium oxide that the reduction peak that occurs at-0.36V can belong to current potential to be formed when just sweeping.
As seen from Figure 3, clearly naked glass-carbon electrode does not have electro catalytic activity to glucose in basic solution, and the modified electrode that preparation also has been described simultaneously comes from the Pd particle to the electro catalytic activity of glucose.
Embodiment 2:
(1) pre-treatment of matrix glass-carbon electrode: with the aluminum oxide powder polishing of 0.05 μ m, the electrode of own polishing first rinses out dirt with deionized water, more successively through 2mol/L sodium hydroxide, analytical pure level ethanol, 2mol/L HCl and intermediate water supersound washing.
(2) preparation of PS template: through dripping the PS bead aqueous solution that is coated with 5 μ L (ultrasonic evenly) on the glass-carbon electrode of pre-treatment, under room temperature, lucifuge was placed 24 hours, then put under 70 ℃ of vacuum drying ovens baking one hour.PS pellet free assembling in this process through forming the large-scale PS template of the clearly demarcated network structure of hole layer by layer on pretreated glass-carbon electrode surface, is conducive to the electrochemical deposition of the palladium particle in the 3rd step.
(3) preparation of nanometer Pd material: the electrode that will deposit the PS film is placed in acid 8mmol/L palladium chloride solution, i-t deposition 3 * 10 under-0.3V
-2The Pd particle of C.Pd ion in this Process liquor is reduced, and forms the Pd nanoparticle.The glass-carbon electrode that has adsorbed the Pd particle is put into tetrahydrofuran (THF), jiggle several under, then rinse well with nitrogen with intermediate water and dry up the Pd particle modified glassy carbon electrode that namely obtains good dispersity.
As working electrode, saturated calomel electrode (SCE) is as supporting electrode with the palladium modified glassy carbon electrode, and platinum plate electrode forms three-electrode system as to electrode; During electro-chemical test, described electrode system is placed in the 0.1mol/L NaOH solution that stirs with constant rate of speed, apply certain voltage on working electrode, record current-time curvel, after background current reaches stable state, add glucose solution with microsyringe, draw this modified electrode for the i-t curve of glucose responding.
As shown in Figure 4, the palladium modified electrode has good detection sensitivity for glucose, just set up the balance of electric current in general time extremely short after adding glucose solution, quite good and its electrochemical response of the stability of step is good linear relationship to glucose concn, linearity range is 1.0-57.3mM, and anti-UA, AP, the AA interference effect is good.
Embodiment 3:
(1) pre-treatment of matrix glass-carbon electrode: with the aluminum oxide powder polishing of 0.05 μ m, the electrode of own polishing first rinses out dirt with deionized water, more successively through 2mol/L sodium hydroxide, analytical pure level ethanol, 2mol/L hydrochloric acid and intermediate water supersound washing.
(2) preparation of PS template: through dripping the PS bead aqueous solution that is coated with 5 μ L (ultrasonic evenly) on the glass-carbon electrode of pre-treatment, under room temperature, lucifuge was placed 24 hours, then put under 70 ℃ of vacuum drying ovens baking one hour.PS pellet free assembling in this process through forming the large-scale PS template of the clearly demarcated network structure of hole layer by layer on pretreated glass-carbon electrode surface, is conducive to the electrochemical deposition of the palladium particle in the 3rd step.
(3) preparation of nanometer Pd material: the electrode that will deposit the PS film is placed in acid 8mmol/L palladium chloride solution, i-t deposition 3 * 10 under-0.3V
-2The Pd particle of C.Pd ion in this Process liquor is reduced, and forms the Pd nanoparticle.The glass-carbon electrode that has adsorbed the Pd particle is put into tetrahydrofuran (THF), jiggle several under, then rinse well with nitrogen with intermediate water and dry up the Pd particle modified glassy carbon electrode that namely obtains good dispersity.
As shown in Figure 5, this experiment is the experiment of having adopted three plasma samples that contain different blood-sugar contents to make in 20ml0.1M NaOH solution.Result shows, prepared Pd (PS)-GC modified electrode is credible to the detected result of actual sample, and relative standard deviation is less and rate of recovery experimental result is satisfactory, illustrates that this method is feasible in the blood sugar test application facet.
Claims (3)
1. can be used as the nanometer Pd material preparation method of non-enzymatic glucose sensor, its step is:
(1) pre-treatment of matrix glass-carbon electrode: with the aluminum oxide powder polishing of electrode with 0.05 μ m, use deionized water rinsing, more successively through 2mol/LNaOH, ethanol, 2mol/L HCl and intermediate water supersound washing;
(2) preparation of PS template: drip the PS bead aqueous solution that is coated with 5 microlitres on the matrix glass-carbon electrode that step (1) is processed, under room temperature, lucifuge is placed, then puts into oven dry under 70 ℃ of vacuum drying ovens;
(3) preparation of nanometer Pd material: the matrix glass-carbon electrode that step (2) is obtained is placed in acid PdCl2 solution, under-0.3V, i-t deposits the Pd particle of 0.03 coulomb, jiggle, then rinse well to dry up with nitrogen with intermediate water and namely obtain nanometer Pd material.
2. nanometer Pd material according to claim 1 as the application of non-enzymatic glucose sensor, is characterized in that nanometer Pd material is directly used in as the enzyme-free glucose amperometric biosensor test of glucose concn.
3. nanometer Pd material according to claim 2 is as the application of non-enzymatic glucose sensor, it is characterized in that testing method is: with the nanometer Pd material modified glassy carbon electrode as working electrode, saturated calomel electrode is as supporting electrode, and platinum plate electrode forms three-electrode system as to electrode; During electro-chemical test, described three-electrode system is placed in the 0.1mol/L sodium hydroxide solution that stirs with constant rate of speed, apply certain voltage on working electrode, record current-time curvel, after background current reaches stable state, add glucose solution with microsyringe, draw this modified electrode for the i-t curve of glucose responding.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105717183A (en) * | 2016-03-22 | 2016-06-29 | 扬州大学 | Non-enzyme glucose sensor and manufacturing method thereof |
| CN106770598A (en) * | 2016-12-08 | 2017-05-31 | 东莞理工学院 | Pd nano wire modified electrodes and its production and use |
| CN107486562A (en) * | 2017-11-09 | 2017-12-19 | 西北师范大学 | Plant-derived polyoses extract reducing metal salt prepares method and the application of metal nano material |
| CN110923130A (en) * | 2019-10-14 | 2020-03-27 | 嘉兴学院 | Microbial sensor and preparation method and application thereof |
| TWI775809B (en) * | 2017-02-10 | 2022-09-01 | 美商伊士曼化學公司 | Electrode for electrochemical sensors |
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| CN101320036A (en) * | 2008-07-01 | 2008-12-10 | 南京师范大学 | Detection method of non-enzyme glucose |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105717183A (en) * | 2016-03-22 | 2016-06-29 | 扬州大学 | Non-enzyme glucose sensor and manufacturing method thereof |
| CN106770598A (en) * | 2016-12-08 | 2017-05-31 | 东莞理工学院 | Pd nano wire modified electrodes and its production and use |
| CN106770598B (en) * | 2016-12-08 | 2019-06-04 | 东莞理工学院 | Pd nano wire modified electrode and its preparation method and application |
| TWI775809B (en) * | 2017-02-10 | 2022-09-01 | 美商伊士曼化學公司 | Electrode for electrochemical sensors |
| US11561220B2 (en) | 2017-02-10 | 2023-01-24 | Eastman Chemical Company | Electrode for electrochemical sensors |
| CN107486562A (en) * | 2017-11-09 | 2017-12-19 | 西北师范大学 | Plant-derived polyoses extract reducing metal salt prepares method and the application of metal nano material |
| CN110923130A (en) * | 2019-10-14 | 2020-03-27 | 嘉兴学院 | Microbial sensor and preparation method and application thereof |
| CN110923130B (en) * | 2019-10-14 | 2023-08-18 | 嘉兴学院 | Microbial sensor and preparation method and application thereof |
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Application publication date: 20130515 |