CN103194774A - Preparation method and use of Pd nano-rod array/sol-gel membrane-modified electrode - Google Patents
Preparation method and use of Pd nano-rod array/sol-gel membrane-modified electrode Download PDFInfo
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- CN103194774A CN103194774A CN201210059096XA CN201210059096A CN103194774A CN 103194774 A CN103194774 A CN 103194774A CN 201210059096X A CN201210059096X A CN 201210059096XA CN 201210059096 A CN201210059096 A CN 201210059096A CN 103194774 A CN103194774 A CN 103194774A
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Abstract
The invention provides a preparation method and a use of a Pd nano-rod array/sol-gel membrane-modified electrode. The preparation method comprises the following steps of 1, preparing an alcohol-water solution of TEOS, HCl, CTAB, PdCl2 and a sodium salt or a potassium salt to obtain a sol system, wherein a volume ratio of alcohol to water is in a range of 1/2 to 2; a TEOS concentration is in a range of 100 to 150mM; a sodium salt or potassium salt concentration is in a range of 50 to 100mM; a CTAB concentration is in a range of 3 to 8mM; a HCl concentration is in a range of 4 to 10mM; and a PdCl2 mass concentration percentage is in a range of 0.01 to 0.03%, 2, immersing a working electrode in the sol system and carrying out deposition in the potential of -1 to -1.3V for 40 to 80s, and 3, after the deposition, taking out the working electrode, and carrying out water punching and air drying to obtain the Pd nano-rod array/sol-gel membrane-modified electrode. The invention also provides a use of the Pd nano-rod array/sol-gel membrane-modified electrode in separation and detection.
Description
Technical field
The invention belongs to sensor field, be specifically related to the preparation method and application of a kind of Pd nanometer stick array/sol gel film modified electrode.
Background technology
Biosensor is the functional device that bio-identification unit and signal conversion element are coupled formation, with the biological activity unit as bio-sensitive film.At present, the biosensor research field subject matter that need solve is how to improve interface controllability and circulation ratio.Obtain highly sensitive, tolerance range is high, cost is low, high-throughout biosensor, the structure that chemistry is controlled, bio-compatibility good, be conducive to the sensing interface of interfacial mass transfer is crucial.Different base active membrane material has important use in the preparation of different sorts sensor.Film has not only improved the conductive process of electrical signal, and has increased the fixed amount of biomolecules, thereby influences the performance of sensor.
The application of sol-gel derived thing material in biosensor obtained extensive concern.Because it not only has good bio-compatibility and character such as unreactiveness, thermostability, and silicon and organosilicone film at room temperature can prepare at electrode surface.This film can contain suitable organosilane monomer by dip-coating or spin coating usually, induces at the substrate surface hydrolytic polymerization by evaporation.This method is simple to operate, but have also that film thickness is uncontrollable, the easy embrittlement of gel-film, the shortcoming such as insecure of being combined with the metal electrode substrate, hindered electron transfer efficiency and the molecular mass-transfer process of film, and this kind method only limits at the flat base surface filming.By controlling sol-gel process step by step with electrochemical deposition method, namely apply a negative potential in electrode/solution surface, generation OH-makes (only making) thereby electrode/solution surface pH rising quickening polymerization process can generate the silicon sol-gel film.This silicon sol-gel film only can form along conductive substrates, so not only can realize the controlled preparation of electrochemistry of sol gel film but also can be implemented in uneven suprabasil preparation.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective of prior art, and the preparation method and application of a kind of Pd nanometer stick array/sol gel film modified electrode are provided.
The present invention is achieved in that the preparation method of a kind of Pd nanometer stick array/sol gel film modified electrode, and it comprises the steps:
Preparation TEOS, sodium salt or sylvite, HCl, CTAB and PdCl
2Alcohol solution, get sol system, wherein, the volume ratio of alcohol and water is 1/2～2; The concentration of TEOS is 100～150mM, and the concentration of sodium salt or sylvite is 50～100mM, and the concentration of CTAB is 3～8mM, and the concentration of HCl is 4～10mM, PdCl
2The quality solubility of solution is 0.01%～0.03%;
Working electrode is immersed described sol system ,-1～-current potential deposit 40～80S of 1.3V.After deposition finishes electrode is taken out, the water flushing is dried, and obtains Pd nanometer stick array/sol gel film modified electrode.
And, the application of Pd nanometer stick array/sol gel film modified electrode that the preparation method of above-mentioned Pd nanometer stick array/sol gel film modified electrode obtains in separating and detecting.
The preparation method of Pd nanometer stick array of the present invention/sol gel film modified electrode is electro-deposition method, adopt the prepared Pd nanometer stick array of this method to have orderly structure, the direction of growth is perpendicular to electrode surface, and the preparation method is simple, and be generalized in other metallic substance nanometer stick arrays synthetic, prepared Pd nanometer stick array/sol gel film is widely used in separating and detecting.
Description of drawings
Fig. 1 is the low-resolution scan Electronic Speculum figure of the Pd nanometer stick array/sol gel film modified electrode of the embodiment of the invention 1 preparation;
Fig. 2 is the high resolution scanning Electronic Speculum figure of the Pd nanometer stick array/sol gel film modified electrode of the embodiment of the invention 1 preparation;
Fig. 3 is the sem photograph of the sol gel film modified electrode of Comparative Examples 1 preparation of the present invention;
Fig. 4 is 100mVs
-1Sweep speed down, the cyclic voltammogram of sol gel film modified electrode in the 0.1M NaOH solution that contains 0mM (a) and 5mM (b) glucose of Comparative Examples 1 preparation of the present invention;
Fig. 5 is 100mVs
-1Sweep speed down, the cyclic voltammogram of Pd nanometer stick array/sol gel film modified electrode in the 0.1M NaOH solution that contains 0mM (a) and 5mM (b) glucose;
Fig. 6 is 100mVs
-1Sweep speed down, the cyclic voltammogram of Pd nanometer stick array/sol gel film modified electrode continuous sweep 50 circles in containing the 0.1M NaOH solution of 5mM glucose;
Fig. 7 is that Pd nanometer stick array/sol gel film modified electrode is to the cyclic voltammogram of 0mM, 2mM, 4mM, 6mM, 8mM, 10mM (from a to f) glucose responding;
Fig. 8 is when the detection current potential is 0V, and Pd nanometer stick array/sol gel film modified electrode is to the instant current-responsive figure of continuous adding 0.5mM glucose, and interior illustration is calibration curve;
Fig. 9 is sol gel film modified electrode (a), naked glass-carbon electrode (b), and Pd nanometer stick array/sol gel film modified electrode (c) is containing 200 μ M xitix, the differential pulse voltammogram in the coexistence system of 150 μ M Dopamine HCLs and 150 μ M uric acid;
Figure 10 is that Pd nanometer stick array/sol gel film modified electrode is containing 200 μ M xitix, in the mixed system of 100 μ M uric acid to 30 μ M, 60 μ M, 90 μ M, the differential pulse voltammogram of 120 μ M and 150 μ M (from a to e) Dopamine HCLs response;
Figure 11 is that Pd nanometer stick array/sol gel film modified electrode is containing 200 μ M xitix, 100
In the mixed system of M Dopamine HCL to 10 μ M, 70 μ M, 130 μ M, the differential pulse voltammogram of 190 μ M and 250 μ M (from a to e) uric acid response.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The embodiment of the invention is achieved in that the preparation method that a kind of Pd nanometer stick array/sol gel film modified electrode is provided, and this method comprises the steps:
S01: preparation TEOS, sodium salt or sylvite, HCl, CTAB and PdCl
2Alcohol solution, get sol system, wherein, the volume ratio of alcohol and water is 1/2～2; The concentration of TEOS is 100～150mM, and the concentration of sodium salt or sylvite is 50～100mM, and the concentration of CTAB is 3～8mM, and the concentration of HCl is 4～10mM, PdCl
2The quality solubility of solution is 0.01%～0.03%;
S02: working electrode is immersed described sol system ,-1～-current potential deposit 40～80S of 1.3V.After deposition finishes electrode is taken out, the water flushing is dried, and obtains Pd nanometer stick array/sol gel film modified electrode.
Among the step S01, alcohol solution is preferably the mixing solutions of second alcohol and water, and the volume ratio of second alcohol and water is 1: 1.TEOS hydrolysis in the presence of HCl in precursor ethanol solution; Sylvite and sodium salt are saltpetre or SODIUMNITRATE; The concentration of CTAB is preferably 4～6mM; The concentration of HCl is preferably 5～7mM.Further, described working electrode is naked glass-carbon electrode, the glass-carbon electrode of in sand paper and oxidation aluminium paste, polishing, and difference ultrasonic cleaning 5min in acetone, ethanol uses the distilled water ultrasonic cleaning at last then, namely obtains the clean naked glass-carbon electrode of surface treatment.
Among the step S02, under the negative pole current potential, working electrode and the pH of solution interface place raise, and induce Pd nanometer rod orientation perpendicular to glass-carbon electrode growth and homogeneous, accumulation in order on sol gel film.Pd nanometer rod diameter is about 40～60nm, and length is between 200～300nm.The growth of this Pd nanometer stick array has proved well-regulated mesoporous passage on sol gel film.
Pd nanometer stick array/sol gel film modified electrode that the preparation method of Pd nanometer stick array/sol gel film modified electrode that the embodiment of the invention provides is prepared, the length of Pd nanometer rod can change with the change of electrodeposition time.This ordered nano bar structure has taken full advantage of the big specific surface area of nano material, be conducive to detect fully contacting of substrate and nano material, improve detection sensitivity greatly, can realize the direct detection to glucose, and noiseless detection Dopamine HCL and uric acid.
Below by specific embodiment the preparation method and application of above-mentioned Pd nanometer stick array/sol gel film modified electrode are described.
Embodiment 1:
Add 150 μ L TEOS, 20mL ethanol, 20mL in the 50mL beaker successively and contain 0.1MNaNO
3With the aqueous solution, the 240 μ L HCl (0.1M) of 10mM CTAB, the PdCl of 1mL 1% (w/w)
2Solution mixes, and stirs 4 hours under the room temperature.Then working electrode is immersed the sol system prepare, at the current potential deposit 60S of-1.3V.After deposition finishes electrode is taken out, also at room temperature dry naturally with the redistilled water flushing.Namely prepare Pd nanometer stick array/sol gel film modified electrode, see also illustrated in figures 1 and 2.
Embodiment 2:
Add 120 μ L TEOS, 20mL ethanol, 20mL in the 50mL beaker successively and contain 0.1MKNO
3With the aqueous solution, the 200 μ L HCl (0.1M) of 8mM CTAB, the PdCl of 1mL 1% (w/w)
2Solution mixes, and stirs 4 hours under the room temperature.Then working electrode is immersed the sol system prepare, at the current potential deposit 80S of-1.3V.After deposition finishes electrode is taken out, also at room temperature dry naturally with the redistilled water flushing.Namely prepare Pd nanometer stick array/sol gel film modified electrode.
Embodiment 3:
Add 200 μ L TEOS, 20mL ethanol, 20mL in the 50mL beaker successively and contain 0.1MNaNO
3With the aqueous solution, the 300 μ L HCl (0.1M) of 12mM CTAB, the PdCl of 1mL 1% (w/w)
2Solution mixes, and stirs 4 hours under the room temperature.Then working electrode is immersed the sol system prepare, at the current potential deposit 40S of-1.3V.After deposition finishes electrode is taken out, also at room temperature dry naturally with the redistilled water flushing.Namely prepare Pd nanometer stick array/sol gel film modified electrode.
Comparative Examples 1
Add 150 μ L TEOS, 20mL ethanol, 20mL in the 50mL beaker successively and contain 0.1MNaNO
3The aqueous solution, 240 μ L HCl (0.1M) with 10mM CTAB mix, and stir 4 hours under the room temperature.Then working electrode is immersed the sol system prepare, at the current potential deposit 60S of-1.3V.After deposition finishes electrode is taken out, also at room temperature dry naturally with the redistilled water flushing.Namely prepare the sol gel film modified electrode, see also shown in Figure 3.
Pd nanometer stick array/sol gel film modified electrode that the preparation method of present embodiment Pd nanometer stick array/sol gel film modified electrode obtains is applied to separate and detect.Pd nanometer stick array/sol gel film modified electrode can not have enzyme to glucose and detects, and synchronous, the noiseless detection of Dopamine HCL (DA) and uric acid (UA).The sol gel film modified electrode that adopts Comparative Examples 1 preparation is used for that glucose is not had enzyme to be detected.In liquid at the bottom of the 0.1M NaOH, the sol gel film modified electrode does not have tangible cyclic voltammetric response change to 0mM (a) and 5mM (b) glucose, sees also Fig. 4.This shows that simple silicon sol-gel film does not have the catalytic oxidation effect to glucose.As shown in Figure 5, be apparent that in contrast Pd nanometer stick array/sol gel film modified electrode is to obvious to the cyclic voltammetric response change of 0mM (a) and 5mM (b) glucose.After buffer system adds 5mM (b) glucose, can be observed two obvious sharp-pointed anodic peak current to appear at-0.05V and-0.35V, this is because the catalytic oxidation of the glucose of Pd produces.The obvious cause of increased of electrical signal is that a large amount of Pd is fixed in the sol gel film behind the adding glucose.And, be conducive to contacting between Pd and the glucose perpendicular to the Pd nanometer stick array of substrate.
Fig. 6 has shown the cyclic voltammogram of Pd nanometer stick array/sol gel film modified electrode continuous sweep 50 circles in containing the 0.1M NaOH solution of 5mM glucose.As can be seen from Figure 6, in the process of continuous sweep 50 circles, any change does not almost take place in cyclic voltammetry curve, and this has shown that this Pd nanometer stick array/sol gel film modified electrode has satisfactory stability.After detection is finished, electrode soaked in damping fluid, place 4 ℃ to preserve down.Carry out test experience and initial experimental signal basically identical after one month again.
Fig. 7 shown Pd nanometer stick array/sol gel film modified electrode to 0,2,4,6,8, the cyclic voltammogram of 10mM (from a to f) glucose responding.Fig. 8 is when the detection current potential is 0V, and Pd nanometer stick array/sol gel film modified electrode is to the instant current-responsive figure of continuous adding 0.5mM glucose, and interior illustration is calibration curve.After adding glucose in the system, electrical signal tends towards stability in 5S.When glucose concn arrived 10mM at 0.05mM, electrical signal and concentration were the linear dependence relation, were limited to 10 μ M (S/N=3) under detecting.
Stability and circulation ratio are the important indicators of evaluation sensor performance and actual application value.For estimating the stability of this sensor, 1 sensor of continuous ten detections is to the response of 1mM glucose, and relative standard deviation (RSD) is 4.7%.Be the circulation ratio of verificating sensor, prepare 6 sensors under the same conditions, and detect the response to 1mM glucose respectively, relative standard deviation (RSD) is 6.7%.Satisfactory stability and circulation ratio have shown the reliability of sensor.
Dopamine HCL (DA), uric acid (UA) and xitix (AA) are biomolecules important in the body fluid, and the three is very approaching at the oxidizing potential of electrode surface.Because be not easy three's peak current separately, so realize that in the mixed system of Dopamine HCL, uric acid and xitix coexistence the detection of Dopamine HCL and uric acid is difficult.With the Pd nanometer stick array/sol gel film modified electrode that adopts method for preparing be used for Dopamine HCL, uric acid and xitix coexistence system Dopamine HCL and uric acid synchronous detection.With differential pulse voltammetry (DPV) respectively to sol gel film modified electrode (a), naked glass-carbon electrode (b), the electrochemical behavior of Pd nanometer stick array/sol gel film modified electrode (c) is studied.Among Fig. 9, containing 200 μ M xitix, in the mixing coexistence system of 150 μ M Dopamine HCLs and 150 μ M uric acid, naked glass-carbon electrode can only have two differential pulse volt-ampere peak currents at 0.14V and 0.31V place, it is overlapping that this shows that the peak current of xitix and Dopamine HCL has taken place, shown in curve b.At electrode modification after the sol gel film, peak current disappears, these may be owing to the insulating property of silicon fiml, shown in curve a.On the contrary, on Pd nanometer stick array/sol gel film modified electrode, can be observed 3 clear and legible current peak, xitix, Dopamine HCL and uric acid current peak separately is respectively at 0mV, and 160mV and 300mV current potential place occur, shown in curve c.Xitix, the peak of Dopamine HCL and uric acid separates potential difference up to 160mV and 140mV.Except the peak obviously separated, the response sensitivity of three kinds of biomolecules increased simultaneously.
Because Pd nanometer stick array/sol gel film modified electrode can separate xitix preferably, the spike potential of Dopamine HCL and uric acid, in three's coexistence system, it is constant to fix other two kinds of concentration of component, and Dopamine HCL or uric acid are carried out Electrochemical Detection.As shown in figure 10, contain 200 μ M xitix and 100 μ M uric acid in the PBS damping fluid, the concentration of Dopamine HCL is increased to 150 μ M from 30 μ M, and differential pulse volt-ampere curve shows that the peak current of Dopamine HCL constantly increases (from a to e).Meanwhile, both peak currents remain unchanged substantially in addition.As shown in figure 11, fixedly the concentration of xitix and Dopamine HCL is respectively 200 μ M and 100 μ M, and when the concentration of uric acid was increased to 250 μ M from 10 μ M, the peak current of uric acid constantly increased (from a to e), and both peak point currents do not have to change substantially in addition.The above results shows, in the coexistence system of three kinds of biomolecules, can realize synchronous detection Dopamine HCL or uric acid, and other two kinds of components can not disturbed detecting to produce in the system.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of Pd nanometer stick array/sol gel film modified electrode is characterized in that, comprises the steps:
Preparation TEOS, sodium salt or sylvite, HCl, CTAB and PdCl
2Alcohol solution, get sol system, wherein, the volume ratio of alcohol and water is 1/2～2; The concentration of TEOS is 100～150mM, and the concentration of sodium salt or sylvite is 50～100mM, and the concentration of CTAB is 3～8mM, and the concentration of HCl is 4～10mM, PdCl
2The quality solubility of solution is 0.01%～0.03%;
Working electrode is immersed described sol system ,-1～-current potential deposit 40～80S of 1.3V.After deposition finishes electrode is taken out, the water flushing is dried, and obtains Pd nanometer stick array/sol gel film modified electrode.
2. the preparation method of Pd nanometer stick array as claimed in claim 1/sol gel film modified electrode is characterized in that, alcohol solution is the mixing solutions of second alcohol and water.
3. the preparation method of Pd nanometer stick array as claimed in claim 2/sol gel film modified electrode is characterized in that, the volume ratio of described second alcohol and water is 1: 1.
4. the preparation method of Pd nanometer stick array as claimed in claim 1/sol gel film modified electrode is characterized in that, the diameter of Pd nanometer rod is 40～60nm in the Pd nanometer stick array, and length is 200～300nm.
5. the preparation method of Pd nanometer stick array as claimed in claim 1/sol gel film modified electrode is characterized in that, described sylvite and sodium salt are saltpetre or SODIUMNITRATE.
6. the preparation method of Pd nanometer stick array as claimed in claim 1/sol gel film modified electrode is characterized in that, the concentration of described CTAB is 4～6mM.
7. the preparation method of Pd nanometer stick array as claimed in claim 1/sol gel film modified electrode is characterized in that, the concentration of described HCl is 5～7mM.
8. the application of Pd nanometer stick array/sol gel film modified electrode in separating and detecting that obtains as the preparation method of the described Pd nanometer stick array of claim 1～7/sol gel film modified electrode.
9. the Pd nanometer stick array/sol gel film modified electrode that obtains as the preparation method of the described Pd nanometer stick array of claim 1～7/sol gel film modified electrode does not have the application of enzyme in detecting at glucose.
10. the application of the Pd nanometer stick array/sol gel film modified electrode that obtains as the preparation method of the described Pd nanometer stick array of claim 1～7/sol gel film modified electrode in Dopamine HCL and uric acid detect.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109164153A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | Rhodamine 6G-palladium membranes modification ITO electrode preparation method and applications |
| CN114011372A (en) * | 2021-11-30 | 2022-02-08 | 齐鲁工业大学 | Bifunctional microstructure palladium-based membrane reactor and preparation method thereof |
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| US20080241755A1 (en) * | 2007-02-01 | 2008-10-02 | Franklin Aaron D | Contact metallization of carbon nanotubes |
| CN102050955A (en) * | 2009-10-28 | 2011-05-11 | 北京化工大学 | Preparation method of polystyrene-based mesoporous silica film |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109164153A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | Rhodamine 6G-palladium membranes modification ITO electrode preparation method and applications |
| CN114011372A (en) * | 2021-11-30 | 2022-02-08 | 齐鲁工业大学 | Bifunctional microstructure palladium-based membrane reactor and preparation method thereof |
| CN114011372B (en) * | 2021-11-30 | 2023-03-17 | 齐鲁工业大学 | Difunctional microstructure palladium-based membrane reactor and preparation method thereof |
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