CN106770598A - Pd nano wire modified electrodes and its production and use - Google Patents
Pd nano wire modified electrodes and its production and use Download PDFInfo
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Abstract
The present invention relates to electrochemical field, and in particular to Pd nano wire modified electrodes and its production and use, the preparation method of Pd nano wire modified electrodes is comprised the following steps, AAO templates are 1. prepared, conductive treatment is carried out after AAO template bilaterals；2. by step 1. in bilateral AAO templates be attached to Pt electrode surfaces, carry out DC electrodeposition so that AAO templates are fixed on Pt electrode surfaces；3. the Pt electrodes that surface is fixed with AAO templates are submerged in solution, takes the electrode washing after submergence and obtain orderly PdNAs, dried in the shade, obtain final product Pd nano wire modified electrodes.When detecting the concentration of 2,4 thiazolidinediones using Pd nano wires modified electrode of the invention, detection sensitivity is high, the range of linearity is wide, LDL is low, and strong antijamming capability, accuracy of detection is high.
Description
Technical field
The present invention relates to electrochemical field, more particularly to a kind of Pd nano wires modified electrode and preparation method thereof and use
On the way.
Background technology
Diabetes are global frequently-occurring disease and common disease, with the improvement of people ' s living standards with the increasing of elderly population
Many, its incidence of disease is in obvious ascendant trend.The whole world there are about patient more than 200,000,000, it has also become global health care issues, and
The health of the mankind is seriously threaten, as the third-largest dangerous diseases for being only second to cardiovascular disease, cancer.China there are about now
50000000 patients.Thus, it is also the key subjects that world-wide medical interface is faced that the diagnosis and treatment of diabetes are not only China.
Thiazolidinediones (TZDs) medicine is the medicine of the new treatment type II diabetes of a class and insulin resistance, while
With good tolerance and security, with the potentiality for delaying diabetes development and huge application prospect, except with above-mentioned
Effect is outer, and it shows certain treatment prospect, 2,4- in angiocardiopathy, the warm invention such as nest syndrome and some tumours of many capsules
Thiazolidinedione is the important intermediate of synthetizing thiazolium alkane diones (TZDs) medicine, is also that activity on this kind of medicines structure is determined
Site, therefore significant is detected to it, but detection of the prior art to 2,4- thiazolidinediones is rarely reported.
The content of the invention
To solve the above problems, a kind of sensitivity of present invention offer is high, the range of linearity is wide, LDL is low Pd nanometers
Line modified electrode and its production and use.
The technical solution adopted in the present invention is：The preparation method of Pd nano wire modified electrodes, comprises the following steps, and 1. makes
Standby AAO templates, conductive treatment is carried out after AAO template bilaterals；2. by step 1. in bilateral AAO templates be attached to Pt electrode tables
Face, carries out DC electrodeposition so that AAO templates are fixed on Pt electrode surfaces；3. surface is fixed with the Pt electrodes of AAO templates in
Submerged in solution, take the electrode washing after submergence and obtain orderly PdNAs, dried in the shade, obtain final product Pd nano wire modified electrodes.
To being further improved to for above-mentioned technical proposal, step 1. in, the preparation method of AAO templates is secondary anode
Method.
To being further improved to for above-mentioned technical proposal, step 2. in, bilateral AAO template epoxy resin is affixed on Pt electrodes
Surface.
To being further improved to for above-mentioned technical proposal, step 2. in, deposition voltage be -1.7V~0V.
To being further improved to for above-mentioned technical proposal, step 2. in, deposited electrolyte is for 3.65g/L~5.65g/L
The mixed liquor of the NH4Cl of Pd (NH3) 4Cl2 and 15g/L~30g/L, the pH of deposited electrolyte is 7.0~9.0.
To being further improved to for above-mentioned technical proposal, step 3. in, submerged with the NaOH solution of 2M and be fixed with AAO templates
Pt electrodes, Immersion time be 30min~50min, rinse electrode water be redistilled water.
Pd nano wire modified electrodes, are obtained using the preparation method any one of claim 1~6.
The purposes of Pd nano wire modified electrodes, it is characterised in that：With the Pd nano wire modified electrodes described in claim 7
Detect the concentration of 2,4- thiazolidinediones.
To being further improved to for above-mentioned technical proposal, 2,4- thiazolidinedione solution is taken, with Pd nano wire modified electrodes
It is working electrode, is bottom liquid with PBS, meet with a response letter is detected to 2,4- thiazolidinedione solution using cyclic voltammetry
Number with the linear relationship of 2,4- thiazolidinedione concentration, then contrast test is carried out to interfering material using cyclic voltammetry.
To being further improved to for above-mentioned technical proposal, the concentration of PBS bottoms liquid is 0.2M.
Beneficial effects of the present invention are：
1st, using preparation method of the invention, successfully Pt electrodes can be modified, obtains Pd nano wire modified electrodes, phase
For the glass-carbon electrode of traditional unmodified Pd nano wires, the modified electrode electro catalytic activity area that this preparation method is obtained is big,
Interface electron transport speed with substrate is fast, when 2,4- thiazolidinedione concentration is detected, with more preferable current-responsive and compared with
Sensitivity high, the range of linearity wider and relatively low LDL.
2nd, the preparation method of AAO templates be secondary anode method, first aluminium flake is annealed, clean degreasing, polishing before
Treatment, then carry out an anodic oxidation, remove removing oxide layer, two-step anodization, finally post-processed, that is, go aluminium base, go resistance
Barrier and through hole.Comprise the following steps that：
(1) anneal
The thick high-purity aluminium flakes of 0.3mm are cut into the square sheets of 5cm*5cm specifications, are put into high at 500 DEG C in Muffle furnace
Temperature calcining 4 hours, then naturally cools to room temperature, and mark positive and negative takes out.The inside made annealing treatment by eliminating aluminum substrate should
Power and defect, are conducive to aluminium atom to arrange more in order, so that the arrangement of subsequent oxidation process mesopore is more orderly.
(2) degreasing is cleaned
It is cleaned by ultrasonic 5min during aluminium flake after annealing is sequentially placed into acetone, ethanol, removes the grease of aluminum flake surface, then uses
Redistilled water is rinsed well, is dried.
(3) polish
Aluminium flake polishing is that in order that aluminum flake surface is more bright smooth, the mode of polishing has various, including mechanical polishing, is changed
Optical polishing and electrochemical polish.Wherein, electrochemical polish is because simple to operate, pollution is small, polishing effect is significantly generally made
With.Electro-chemical polish step of the present invention is：Under 20V DC voltages, with aluminium flake as anode, stainless steel substrates are that (aluminium flake is just for negative electrode
Face is just to negative electrode), constant pressure polishing 3min or so comes off until the oxide layer of aluminum flake surface, and aluminum flake surface exposes fresh bright mirror
Face.Wherein, the component of polishing fluid is perchloric acid:Absolute ethyl alcohol=1:6(v:V) mixed solution.Polishing process will be in 0 DEG C of water-bath
In come released in reduction process it is a large amount of to invent influence.Meanwhile, polishing process is unsuitable long, otherwise can be because of polished
Electric current excessive in journey produces punch-through.
(4) anodic oxidations
A thin layer of vaseline will be coated below aluminium flake polished backside boundary line after polishing, be then with aluminium flake
Anode, stainless steel substrates are negative electrode (wet look is just to negative electrode), and regulation D.C. regulated power supply output voltage and controlling reaction temperature are 5
DEG C, the constant voltage oxidation 2h in the oxalic acid solution of 0.3M.Applying last layer vaseline at the aluminium flake back side can effectively prevent back aluminium
Piece participates in anodization, and then limits because the increase of anodization current causes that electrolyte temperature rises, and causes anodization to fail, together
When can simplify the last handling process of aluminium base.
(5) removal of oxide layer
First time anodic oxidation will generally be corroded in the oxide-film that aluminum flake surface is formed, because now nano-pore is orderly
Than relatively low, aperture varies degree, and pattern is poor.The bowl pockets of ordered arrangement can be left through the aluminium surface after excessive erosion, is
Second anodic oxidation generates more orderly alumina formwork and lays the foundation.The present invention is with chromium trioxide (5g/L) and phosphoric acid (body
Fraction 5%) mixed solution be corrosive liquid, control temperature 70 C reaction 1h, with ensure completely removal first set reaction generate
Oxide-film.
(6) two-step anodization
In order to obtain thicker alumina formwork, under the conditions of with first time anodic oxidation identical, the time is carried out more
Second anodic oxidation long.
(7) aluminium base is gone
Aluminium flake after two-step anodization is removed, petrolatum layer is gently scraped off with the scraps of paper, saturation hydrogen-oxygen is dipped with cotton swab
Change sodium solution and gently smear reverse side, the alumina layer a small amount of to remove reverse side.Aluminium flake after treatment is immersed into saturation butter of tin
In solution, treat that aluminium base removal is complete, rinsed well template with redistilled water.Template after removal aluminium base is in fully transparent
Shape, and because the vaseline on aluminium flake back side periphery during secondary anode comes off on a small quantity, cause periphery to be oxidized.Smear hydrogen-oxygen
Peripheral part is left when changing sodium solution, so, is stayed because peripheral part both sides have alumina layer to protect when aluminium base is removed
Lower aluminium circle.The aluminium circle can play a part of stabilization alumina formwork in later application operation, so as to effectively reduce oxidation
The broken probability of aluminum alloy pattern plate.
(8) barrier layer and through hole are removed
Template after removal aluminium base is made up of upper and lower two parts, and upper strata is the loose pore passage structure of ordered arrangement, and lower floor is
One layer of dense barrier layer of duct bottom.The barrier layer is non-conductive, if for must be driven off if preparing metal nanometer line array or
It is thinning.Template is swum on phosphoric acid solution surface, after behind the barrier layer that solution corrosion falls template bottom by capillarity edge
Duct rises, and until solution reaches template upper surface and is finally completely covered, capped template is gradually sunk.Treat that template is sunk
Pressed from both sides out with tweezers afterwards and rinsed well with redistilled water.
Regular orderly AAO templates can be obtained using this method；And used in anode oxidation process in the painting of the aluminium flake back side
The straightforward procedure of a thin layer vaseline is smeared, the oxidation at the aluminium flake back side is effectively prevented, the last handling process of template is simplified；At this
During the AAO template constructs of invention, barrier layer and through hole link are being gone, be that template is swum in into phosphoric acid solution surface, will passed
System immersion through hole mode is changed to float through hole method, and immersion is uniform, be easy to judge and observe template just showing with anti-surface, effectively keep away
Exempt from corrosion of the acid solution to AAO template front surfaces in via process, the original length in template duct remained to greatest extent,.
3rd, bilateral AAO templates epoxy resin is affixed on Pt electrode surfaces, and epoxy resin is non-conductive, good airproof performance, due to
Between only being needed in the electrodes when preparing PdNAs there is electrode reaction in position, if poor sealing, the excessive influence of electric current can be caused
Nano wire, so that accuracy and sensitivity when influenceing Pd nano wire modified electrode Electrochemical Detections.
4th, the preparation for PdNAs uses DC electrodeposition, relative to modified electrode prepared by alternate electrodepostion process, gained
Modified electrode surface it is more smooth, nano wire is seldom reunited, rigidity more preferably.Deposition voltage is -1.7V~0V, preferably -
0.7V, nano wire is rigidly good under this voltage, uniformly, thus accuracy when ensureing Pd nano wire modified electrode Electrochemical Detections and
Sensitivity.
5th, during DC electrodeposition, due to plating palladium liquid in palladium salt species, concentration, ammonium chloride concentration, the concentration of free ammonia, pH value,
Temperature and additive etc. can all influence to plate palladium effect, be the Pd of 3.65g/L~5.65g/L from deposited electrolyte in the present invention
(NH3) mixed liquor of the NH4Cl of 4Cl2 and 15g/L~30g/L, the pH of deposited electrolyte is 7.0~9.0, using deposition electricity
Used as plating palladium liquid, can make AAO form stables is fixed on Pt electrode surfaces to solution liquid, and plating palladium effect is good, and concrete reason is as follows：
(1) palladium salt concentration：
Although the species for plating palladium liquid is a lot, the plating solution gained coating ductility based on Pd (NH3) x is higher.This hair
The bright palladium salt for using be the ammonia palladium of dichloro four (Pd (NH3) 4Cl2), the mass concentration of salt because significantly influenceing cathode-current density,
Should not be excessive, general control is between 10-25g/L (in terms of Pd).When mass concentration is smaller, coating deposition rate is slow, and color and luster is not
Light is uneven or even blacks；Mass concentration is too high, and gained coating is more crisp broken outside increasing production cost.The present invention will
Make palladium salt solution enter nano-pore so that inner hole deposition accumulate, therefore selection further reduce salinity, institute the palladium salt concentration that uses for
2.5g/L (in terms of Pd).
(2) ammonium chloride concentration：
Ammonium chloride plays a part of to increase plating solution electric conductivity and regulation pH value in the plating solution simultaneously, forms slow together with ammoniacal liquor
Fliud flushing.When ammonium chloride mass concentration is between 20-30g/L, Deposit appearance is brighter.And work as the constant ammonium chloride quality of other conditions
When concentration is relatively low, there is white clouds shape decorative pattern in coating surface；Mass concentration is too high, and coating surface can one layer of red film of blackening or generation.
It is 20g/L that the present invention uses ammonium chloride mass concentration.
(3) the concentration of free ammonia：
The concentration of free ammonia is too high, and coating can be covered with the striped or spot of black；It is relatively low, yellow mercury oxide can be produced on negative electrode,
So that coating is coarse, color is colored and uneven.The present invention takes and is adjusted to the direct ammoniacal liquor (34%) that is added dropwise in the plating palladium liquid for preparing
Solution pH value of solution determines the content of free ammonium in plating solution to the mode of desirable value.
(4) pH value：
Usual control ph is between 7.0-9.0.PH value is too high, and coating surface occurs the situation that ammonia is largely escaped；
PH value is too low, and anode easily passivation in place's is outer, there is also the situation of palladium salt Precipitation.Generally plating solution is adjusted with HCl and ammoniacal liquor
PH value.It is 8.3 that the present invention uses pH value.
(5) temperature：
Other timings of technological parameter one, bath temperature can obtain good coating, such as temperature not between 20-50 DEG C
Coordinate, coating deposition rate can be influenceed, the present invention is carried out at room temperature.
(6) additive：
Additive typically refers to the surfactants such as C4-C35 fat straight chain quaternary ammonium salts, and sulfur-bearing organic acid and its salt etc.
Brightener, the heterocyclic compound and poly- disulphide for dredging base etc..Coating light pulls degree, crackle situation occurs and coating crystallization cause
Close degree can be improved because of the use of additive.But the deposition velocity of metal ion can be subject to this kind of organising when adding excessive
The retardance of compound additive, aquation metal ion deposits limited on negative electrode, it is difficult to constitutes the metallic crystal of certain lattice and makes
Black into artistic face.The present invention considers that retardation of the additive in nano-pore is larger, therefore does not use additive.
To sum up, plating palladium liquid composition of the invention is 2.5g/L Pd (NH3) 4Cl2+20g/L NH4Cl, and ammoniacal liquor regulation is added dropwise
PH=8.3.
6th, step 3. in, the preparation method of PdNAs is AC electrodeposition combination template or DC electrodeposition combination template
Method.When AC electrodeposition combination template prepares PdNAs, 0 is depressurized to using the step-decreasing voltage speed of 2V/min, deposition voltage is
10V-14V, sedimentation time and nanowire length positive correlation.Using 2V/min step-decreasing voltage speed the reason for be now template hinder
Barrier thickness is moderate, and nano wire effect is prepared preferably for AC electrodeposition, and deposition voltage can not less than 10V or higher than 14V
PdNAs is obtained, and the PdNAs sequences that voltage is obtained in 10V-14V are preferably, and increase with voltage, deposition in same time
The length of nano wire increases.When DC electrodeposition combination template prepares PdNAs, the nanowire surface for obtaining is more smooth, and receives
Rice noodles rigidity more preferably, still is able to well independently of one another without reuniting when length is up to 4 μm.The nano wire in the range of certain hour
The speed of growth and time positive correlation, deposition 2h can be up to 4 μm of nano wire, space between moderate length, and single nano-wire
Substantially, independence is good.
7th, the Pd nano wire modified electrodes obtained using preparation method of the invention, nano wire is rigidly good, electro catalytic activity
Area is big, and the interface electron transport speed with substrate is fast, when 2,4- thiazolidinedione concentration is detected, is rung with more preferable electric current
Answer and sensitivity higher, the range of linearity wider and relatively low LDL.
When the 8th, detecting the concentration of 2,4- thiazolidinediones using Pd nano wires modified electrode of the invention, TZD concentration is in 6 μ
When in the range of M-200 μM, there is good linear relationship (y (μ A)=0.4062C in the response signal of gained with the concentration of glucose
+ 28.84), its coefficient correlation is R=0.998, and the lower limit for detecting TZD concentration is 0.02 μM, and several interfering materials, such as methose
Rather, Metformin hydrochloride, the response signal to prepared Pd nano wire modified electrodes is far below TZD to prepared Pd nanometers
Line modified electrode response signal, therefore detection sensitivity is high, the range of linearity is wide, LDL is low, strong antijamming capability, detection
High precision.
Specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1：The preparation method of Pd nano wire modified electrodes
1. AAO templates are prepared using secondary anode method, conductive treatment is carried out after AAO template bilaterals；
2. by step 1. in bilateral AAO template epoxy resin be affixed on Pt electrode surfaces, carry out DC electrodeposition so that
AAO templates are fixed on Pt electrode surfaces, and deposition voltage is -0.7V, and deposited electrolyte is 4.65g L-1Pd(NH3)4Cl2+20g L-1NH4Cl, deposited electrolyte pH are 8.2, and sedimentation time is 2h；
3. the Pt electrodes that surface is fixed with AAO templates are submerged into 40min in the NaOH solution of 2M, takes the electrode after submergence
Rinsed with redistilled water and obtain orderly PdNAs, dried in the shade, obtain final product Pd nano wire modified electrodes.
The specific preparation flow of step 1. middle AAO templates is：
(1) anneal
The thick high-purity aluminium flakes of 0.3mm are cut into the square sheets of 5cm*5cm specifications, are put into high at 500 DEG C in Muffle furnace
Temperature calcining 4 hours, then naturally cools to room temperature, and mark positive and negative takes out.The inside made annealing treatment by eliminating aluminum substrate should
Power and defect, are conducive to aluminium atom to arrange more in order, so that the arrangement of subsequent oxidation process mesopore is more orderly.
(2) degreasing is cleaned
It is cleaned by ultrasonic 5min during aluminium flake after annealing is sequentially placed into acetone, ethanol, removes the grease of aluminum flake surface, then uses
Redistilled water is rinsed well, is dried.
(3) polish
Aluminium flake polishing is that in order that aluminum flake surface is more bright smooth, the mode of polishing has various, including mechanical polishing, is changed
Optical polishing and electrochemical polish.Wherein, electrochemical polish is because simple to operate, pollution is small, polishing effect is significantly generally made
With.Electro-chemical polish step of the present invention is：Under 20V DC voltages, with aluminium flake as anode, stainless steel substrates are that (aluminium flake is just for negative electrode
Face is just to negative electrode), constant pressure polishing 3min or so comes off until the oxide layer of aluminum flake surface, and aluminum flake surface exposes fresh bright mirror
Face.Wherein, the component of polishing fluid is perchloric acid:Absolute ethyl alcohol=1:6(v:V) mixed solution.Polishing process will be in 0 DEG C of water-bath
In come released in reduction process it is a large amount of to invent influence.Meanwhile, polishing process is unsuitable long, otherwise can be because of polished
Electric current excessive in journey produces punch-through.
(4) anodic oxidations
A thin layer of vaseline will be coated below aluminium flake polished backside boundary line after polishing, be then with aluminium flake
Anode, stainless steel substrates are negative electrode (wet look is just to negative electrode), and regulation D.C. regulated power supply output voltage and controlling reaction temperature are 5
DEG C, the constant voltage oxidation 2h in the oxalic acid solution of 0.3M.Applying last layer vaseline at the aluminium flake back side can effectively prevent back aluminium
Piece participates in anodization, and then limits because the increase of anodization current causes that electrolyte temperature rises, and causes anodization to fail, together
When can simplify the last handling process of aluminium base.
(5) removal of oxide layer
First time anodic oxidation will generally be corroded in the oxide-film that aluminum flake surface is formed, because now nano-pore is orderly
Than relatively low, aperture varies degree, and pattern is poor.The bowl pockets of ordered arrangement can be left through the aluminium surface after excessive erosion, is
Second anodic oxidation generates more orderly alumina formwork and lays the foundation.The present invention is with chromium trioxide (5g/L) and phosphoric acid (body
Fraction 5%) mixed solution be corrosive liquid, control temperature 70 C reaction 1h, with ensure completely removal first set reaction generate
Oxide-film.
(6) two-step anodization
In order to obtain thicker alumina formwork, under the conditions of with first time anodic oxidation identical, the time is carried out more
Second anodic oxidation long.
(7) aluminium base is gone
Aluminium flake after two-step anodization is removed, petrolatum layer is gently scraped off with the scraps of paper, saturation hydrogen-oxygen is dipped with cotton swab
Change sodium solution and gently smear reverse side, the alumina layer a small amount of to remove reverse side.Aluminium flake after treatment is immersed into saturation butter of tin
In solution, treat that aluminium base removal is complete, rinsed well template with redistilled water.Template after removal aluminium base is in fully transparent
Shape, and because the vaseline on aluminium flake back side periphery during secondary anode comes off on a small quantity, cause periphery to be oxidized.Smear hydrogen-oxygen
Peripheral part is left when changing sodium solution, so, is stayed because peripheral part both sides have alumina layer to protect when aluminium base is removed
Lower aluminium circle.The aluminium circle can play a part of stabilization alumina formwork in later application operation, so as to effectively reduce oxidation
The broken probability of aluminum alloy pattern plate.
(8) barrier layer and through hole are removed
Template after removal aluminium base is made up of upper and lower two parts, and upper strata is the loose pore passage structure of ordered arrangement, and lower floor is
One layer of dense barrier layer of duct bottom.The barrier layer is non-conductive, if for must be driven off if preparing metal nanometer line array or
It is thinning.Template is swum on phosphoric acid solution surface, after behind the barrier layer that solution corrosion falls template bottom by capillarity edge
Duct rises, and until solution reaches template upper surface and is finally completely covered, capped template is gradually sunk.Treat that template is sunk
Pressed from both sides out with tweezers afterwards and rinsed well with redistilled water.
Embodiment 2：Pd nano wire modified electrodes
The Pd nano wire modified electrodes of the present embodiment, are prepared from using the preparation method in embodiment 1.Embodiment
3：The purposes of Pd nano wire modified electrodes
Pd nano wires modified electrode detects the concentration of 2,4- thiazolidinediones, takes 2,4- thiazolidinedione solution, is received with Pd
Rice noodles modified electrode is working electrode, is bottom liquid with 0.2M PBS, and 2,4- thiazolidinedione solution is entered using cyclic voltammetry
Row detection, the linear relationship of meet with a response signal and 2,4- thiazolidinedione concentration, then using cyclic voltammetry to interfering material,
Tolbutamide, Metformin hydrochloride carries out contrast test.
When TZD concentration is in the range of 6 μM -200 μM, there is good linear pass in the response signal of gained with the concentration of TZD
System (y (μ A)=0.4062C+28.84), its coefficient correlation is R=0.998, and the lower limit for detecting TZD concentration is 0.02 μM.
Several interfering materials are far below sound of the TZD to prepared modified electrode to the response signal of prepared modified electrode
Induction signal.
Embodiment described above only expresses several embodiments of the invention, and its description is more specific and detailed, but simultaneously
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to guarantor of the invention
Shield scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
- The preparation method of 1.Pd nano wire modified electrodes, it is characterised in that：Comprise the following steps, 1. prepare AAO templates, AAO moulds Conductive treatment is carried out after plate bilateral；2. by step 1. in bilateral AAO templates be attached to Pt electrode surfaces, carry out DC electrodeposition So that AAO templates are fixed on Pt electrode surfaces；3. the Pt electrodes that surface is fixed with AAO templates are submerged in solution, takes submergence Electrode washing afterwards obtains orderly PdNAs, dries in the shade, and obtains final product Pd nano wire modified electrodes.
- 2. the preparation method of Pd nano wires modified electrode according to claim 1, it is characterised in that：Step 1. in, AAO moulds The preparation method of plate is secondary anode method.
- 3. the preparation method of Pd nano wires modified electrode according to claim 1, it is characterised in that：Step 2. in, bilateral AAO template epoxy resin is affixed on Pt electrode surfaces.
- 4. the preparation method of Pd nano wires modified electrode according to claim 1, it is characterised in that：Step 2. in, deposition Voltage is -1.7V~0V.
- 5. the preparation method of Pd nano wires modified electrode according to claim 1, it is characterised in that：Step 2. in, deposition Electrolyte is the Pd (NH of 3.65g/L~5.65g/L3)4Cl2With the NH of 15g/L~30g/L4The mixed liquor of Cl, deposited electrolyte PH be 7.0~9.0.
- 6. the preparation method of Pd nano wires modified electrode according to claim 1, it is characterised in that：Step 3. in, use 2M NaOH solution submergence be fixed with the Pt electrodes of AAO templates, Immersion time is 30min~50min, rinses the water of electrode for secondary Distilled water.
- 7.Pd nano wire modified electrodes, are obtained using the preparation method any one of claim 1~6.
- The purposes of 8.Pd nano wire modified electrodes, it is characterised in that：Examined with the Pd nano wires modified electrode described in claim 7 Survey the concentration of 2,4- thiazolidinediones.
- 9. the purposes of Pd nano wires modified electrode according to claim 8, it is characterised in that：Take 2,4- thiazolidinediones molten Liquid, is bottom liquid with PBS with Pd nano wire modified electrodes as working electrode, molten to 2,4- thiazolidinediones using cyclic voltammetry Liquid detected, the linear relationship of meet with a response signal and 2,4- thiazolidinedione concentration, then using cyclic voltammetry to interference Material carries out contrast test.
- 10. the purposes of Pd nano wires modified electrode according to claim 9, it is characterised in that：The concentration of PBS bottoms liquid is 0.2M。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111575761A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Alumina template, highly vertical ordered antimony nanowire array and preparation method thereof |
| CN112880822A (en) * | 2019-11-29 | 2021-06-01 | 中国科学技术大学 | Photoelectrochemical photodetector and preparation method thereof |
| CN113258082A (en) * | 2021-07-14 | 2021-08-13 | 深圳大学 | Platinum-based amorphous alloy nanowire for oxygen reduction catalysis and preparation method thereof |
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| CN109440148A (en) * | 2018-10-29 | 2019-03-08 | 钟祥博谦信息科技有限公司 | A kind of preparation method and applications of palladium cobalt nanowire |
| CN112880822A (en) * | 2019-11-29 | 2021-06-01 | 中国科学技术大学 | Photoelectrochemical photodetector and preparation method thereof |
| WO2021104527A1 (en) * | 2019-11-29 | 2021-06-03 | 中国科学技术大学 | Photoelectrochemical photosensor and preparation method therefor |
| CN111575761A (en) * | 2020-05-26 | 2020-08-25 | 苏州凌威新能源科技有限公司 | Alumina template, highly vertical ordered antimony nanowire array and preparation method thereof |
| CN113258082A (en) * | 2021-07-14 | 2021-08-13 | 深圳大学 | Platinum-based amorphous alloy nanowire for oxygen reduction catalysis and preparation method thereof |
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