CN105738440A - Gold nano array electrode and non-enzyme hydrogen peroxide sensor manufactured by same - Google Patents
Gold nano array electrode and non-enzyme hydrogen peroxide sensor manufactured by same Download PDFInfo
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Abstract
The invention discloses a gold nano array electrode and a non-enzyme hydrogen peroxide sensor manufactured by the same.The gold nano array electrode is prepared by adopting the following steps that a silicon-based single-layer polymer colloidal crystal array is prepared, and a gold film with the thickness of 10-100 nm deposits on the surface of a template by using the silicon-based single-layer polymer colloidal crystal array as the template and adopting a physical deposition method; the template deposited with the gold film is subjected to thermal decomposition and annealing treatment so as to remove the single-layer polymer colloidal crystal array, and a silicon-based gold nano array is obtained; the silicon-based gold nano array directly serves as the gold nano array electrode.The gold nano array electrode is low in detection limit, high in sensitivity and good in stability, and the preparation method is simple, simple and convenient to operate, economical and environmentally-friendly.
Description
Technical field
The present invention relates to nano-electrode material field, particularly relate to the hydrogen peroxide sensor without enzyme of a kind of gold-nano array electrode and preparation thereof.
Background technology
Hydrogen peroxide (H2O2) it is not only intermediate product or raw material that many biological and chemicals react, also it is the by-product of many enzyme reactions in organism, therefore the numerous areas such as food, pharmacy, biological engineering, Clinical Laboratory, Environmental capacity, weaving, papermaking bleaching, sterilization is required for H2O2Concentration detect.
At present, common to H2O2The concentration method that carries out detecting mainly have titrimetry, spectrographic method, fluorescence method, chemistry optical spectroscopy, electrochemical process etc.；In these detection methods, based on catalatic biosensor, there is less costly, easy and simple to handle, fast response time, sensitivity advantages of higher, thus paid close attention to widely.But catalase exist expensive, be fixed to electrode surface with being difficult to, the biological activity of enzyme is subject to the problems such as environmental disturbances, therefore this be in actual applications greatly limited based on catalatic biosensor.
In recent years, noble metal nano particles was widely applied in biochemistry sensing.Such as: gold nano grain has the excellent properties such as specific surface area is big, surface reaction activity is high, Active sites is many, catalytic efficiency is high, high adsorption capacity, therefore gold nano grain creates advantage for developing without enzyme sensor.In the prior art, biosensor based on gold nano grain is all adopt gold nano particle modification electrode, this gold nano particle modification electrode is to be coated with one layer of gold nano grain on existing battery lead plate to be prepared from, its testing result can be subject to existing coating processes considerable restraint (such as: coating the uniformity, coating thickness, the character etc. of coating medicament), therefore existing gold nano particle modification electrode not only detects restriction height, sensitivity is low, poor stability, and its preparation technology needs to arrange special coating link, complicated operation is loaded down with trivial details, equipment cost and human cost are all significantly high.
Summary of the invention
For above-mentioned weak point of the prior art, the invention provides the hydrogen peroxide sensor without enzyme of a kind of gold-nano array electrode and preparation thereof, not only detection limits low, highly sensitive, good stability, and preparation method is simple, easy and simple to handle, with low cost, economic and environment-friendly.
It is an object of the invention to be achieved through the following technical solutions:
A kind of gold-nano array electrode, adopts following steps to be prepared from:
Step A, prepare silica-based single polymer layer crystalline colloidal arrays, and with this silica-based single polymer layer crystalline colloidal arrays for template, adopt physical deposition method to deposit the golden film that a layer thickness is 10～400nm on the surface of described template；
Step B, above-mentioned deposition have the template of golden film thermally decompose and make annealing treatment, to remove single polymer layer crystalline colloidal arrays, thus preparing silica-based gold-nano array；By this silica-based gold-nano array directly as gold-nano array electrode.
Preferably, described silica-based single polymer layer crystalline colloidal arrays of preparing includes: prepares single polymer layer crystalline colloidal arrays on the glass substrate, and tilts to immerse in precursor liquid together with single polymer layer crystalline colloidal arrays by this substrate of glass；Described single polymer layer crystalline colloidal arrays departs from substrate of glass, and swims on precursor liquid liquid level；Silicon chip is adopted to be picked up by the single polymer layer crystalline colloidal arrays swum on precursor liquid liquid level again, thus preparing silica-based single polymer layer crystalline colloidal arrays.
Preferably, the described single polymer layer crystalline colloidal arrays for preparing on the glass substrate comprises the following steps:
Step A1, substrate of glass is sequentially placed in acetone, ethanol, deionized water and carries out ultrasonic cleaning, again the substrate of glass after cleaning is carried out drying and processing, it is then placed in UV ozone cleaning machine irradiation 10～40min, thus obtaining the substrate of glass of surface hydrophilic；
Step A2, step A1 is processed after substrate of glass put into polymeric colloid ball ethanol dilution liquid, and adopt liquid-vapor interface self-assembling method to synthesize single polymer layer crystalline colloidal arrays on the glass substrate.
Preferably, described polymeric colloid ball ethanol dilution liquid adopts following methods to be prepared from: take the polymeric colloid ball suspension that polymeric colloid bulb diameter is 350～1000nm, and mix with ethanol equal-volume, the sonic oscillation carrying out 10～30min again processes, thus preparing finely dispersed polymeric colloid ball ethanol dilution liquid.
Preferably, described physical deposition method includes magnetron sputtering deposition, thermal evaporation deposition or electron-beam evaporation.
Preferably, described have the template of golden film to thermally decompose and make annealing treatment above-mentioned deposition to include: has the template of golden film to put in tube furnace above-mentioned deposition, and under 900 DEG C of air atmospheres heating anneal 2 hours, single polymer layer crystalline colloidal arrays decomposes on silica-based, and the golden film on silica-based can melt, merges, original position solidification, thus forming periodic silica-based gold-nano array.
A kind of without enzyme hydrogen peroxide sensor, adopt the gold-nano array electrode described in the above-mentioned technology program directly as the working electrode that concentration of hydrogen peroxide is detected.
As seen from the above technical solution provided by the invention, the gold-nano array electrode that the embodiment of the present invention provides is with silica-based single polymer layer crystalline colloidal arrays for template, and adopts physical deposition method to deposit the golden film that a layer thickness is 10～400nm on the surface of described template；Then pass through thermal decomposition and annealing remove silica-based on single polymer layer crystalline colloidal arrays, thus preparing periodic silica-based gold-nano array, and this silica-based gold-nano array can directly as the gold-nano array electrode that concentration of hydrogen peroxide is detected, it is not necessary to use other inertia working electrodes.The present invention not only detects low, highly sensitive, the good stability of restriction, and preparation method is simple, easy and simple to handle, economic and environment-friendly.
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme of the embodiment of the present invention, below the accompanying drawing used required during embodiment is described is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawings according to these accompanying drawings.
The schematic flow sheet of the preparation method of the gold-nano array electrode that Fig. 1 provides for the embodiment of the present invention.
Fig. 2 is the silica-based monolayer polystyrene colloid crystal array and the silica-based gold-nano array electron scanning micrograph that shoots and obtain that adopt Sirion200 field emission scanning electron microscope respectively the polystyrene colloid ball suspension being 350nm with diameter in the embodiment of the present invention 1 to be prepared for raw material.
Fig. 3 is for adopting PhilipsX ' Pert type x-ray diffractometer that the end product (period pitch is the nano-array of 350nm) in the embodiment of the present invention 1 is detected, thus the X-ray diffracting spectrum obtained (XRD figure spectrum).
The gold-nano array electrode that period pitch is 350nm prepared in the embodiment of the present invention 1 is respectively put in phosphate buffer and the phosphate buffer containing 5mM hydrogen peroxide by Fig. 4, and carry out C-V characteristic detection, thus the cyclic voltammetry curve comparison diagram obtained.
Fig. 5 is that the gold-nano array electrode that period pitch is 350nm prepared in the embodiment of the present invention 1 is gradually increased the current-vs-time response curve recorded in process at concentration of hydrogen peroxide.
Fig. 6 is the linear relationship chart that the gold-nano array electrode that period pitch is 350nm prepared in the embodiment of the present invention 1 is gradually increased electric current and the concentration of hydrogen peroxide recorded in process at concentration of hydrogen peroxide.
Fig. 7 is the gold-nano array electrode curve chart that electric current changes with pH value at various ph values that period pitch is 350nm prepared in the embodiment of the present invention 1.
Fig. 8 is the gold-nano array electrode curve chart that electric current varies with temperature at different temperatures that period pitch is 350nm prepared in the embodiment of the present invention 1.
Fig. 9 is that the gold-nano array electrode that period pitch is 350nm prepared in the embodiment of the present invention 1 is adding the current-vs-time response curve recorded in disturbance substance process to hydrogen peroxide.
Figure 10 is the electron scanning micrograph adopting Sirion200 field emission scanning electron microscope respectively the polystyrene colloid ball suspension being 500nm, 750nm, 1000nm with diameter in the embodiment of the present invention 1 to be obtained for the silica-based gold-nano array that raw material prepares shoots.
Figure 11 be by the embodiment of the present invention 1 with diameter be 500nm, 750nm, 1000nm polystyrene colloid ball suspension for raw material prepare gold-nano array electrode be respectively put in the phosphate buffer containing 5mM hydrogen peroxide, and carry out C-V characteristic detection, thus the cyclic voltammetry curve comparison diagram obtained.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on embodiments of the invention, the every other embodiment that those of ordinary skill in the art obtain under not paying creative work premise, broadly fall into protection scope of the present invention.
It is described in detail to gold-nano array electrode provided by the present invention and without enzyme hydrogen peroxide sensor below.
A kind of gold-nano array electrode, adopts following steps to be prepared from:
Step A, prepare silica-based single polymer layer crystalline colloidal arrays (such as: this single polymer layer crystalline colloidal arrays can be monolayer polystyrene colloid crystal array, single layer polymethyl methyl ester crystalline colloidal arrays or monolayer polydimethylsiloxane crystalline colloidal arrays), and with this silica-based single polymer layer crystalline colloidal arrays for template, adopt physical deposition method to deposit the golden film that a layer thickness is 10～400nm on the surface of described template.Wherein, described physical deposition method includes magnetron sputtering deposition, thermal evaporation deposition or electron-beam evaporation.
Specifically, described silica-based single polymer layer crystalline colloidal arrays of preparing may comprise steps of:
Step A1, substrate of glass is sequentially placed in acetone, ethanol, deionized water and carries out ultrasonic cleaning, all ultrasonic cleaning 40min in every kind of liquid, again the substrate of glass after cleaning is carried out drying and processing, it is then placed in UV ozone cleaning machine irradiation 10～40min, thus obtaining the substrate of glass of surface hydrophilic.
Step A2, step A1 is processed after substrate of glass put into polymeric colloid ball ethanol dilution liquid (such as: this polymeric colloid ball can adopt polystyrene colloid ball, polymethyl methacrylate colloidal spheres or polydimethylsiloxane colloidal spheres), and adopt liquid-vapor interface self-assembling method to synthesize single polymer layer crystalline colloidal arrays on the glass substrate.In actual applications, take the polymeric colloid ball suspension that polymeric colloid bulb diameter is 350～1000nm, and mix with ethanol equal-volume, then the sonic oscillation carrying out 10～30min processes, thus can be prepared by finely dispersed polymeric colloid ball ethanol dilution liquid；Described polymeric colloid ball suspension can adopt polystyrene colloid ball suspension, polymethyl methacrylate colloidal spheres suspension or the polydimethylsiloxane colloid colloidal spheres suspension bought by commercial means.
Step A3, when preparing after single polymer layer crystalline colloidal arrays on the glass substrate, (this precursor liquid can adopt SDS aqueous solution to tilt to immerse precursor liquid by substrate of glass together with single polymer layer crystalline colloidal arrays, SDS full name sodiumdodecylsulfate, sodiumsalt, Chinese dodecyl sodium sulfate by name) in；Described single polymer layer crystalline colloidal arrays departs from substrate of glass, and swims on precursor liquid liquid level；Adopt silicon chip to be picked up by the single polymer layer crystalline colloidal arrays swum on precursor liquid liquid level again, dry, thus preparing silica-based single polymer layer crystalline colloidal arrays.
Step B, above-mentioned deposition have the template of golden film thermally decompose and make annealing treatment, to remove single polymer layer crystalline colloidal arrays, thus preparing silica-based gold-nano array；By this silica-based gold-nano array directly as gold-nano array electrode.
Specifically, described have the template of golden film to thermally decompose and make annealing treatment to may include that have the template of golden film to put in tube furnace above-mentioned deposition to above-mentioned deposition, and under 900 DEG C of air atmospheres heating anneal 2 hours, single polymer layer crystalline colloidal arrays decomposes on silica-based, and the golden film on silica-based can melt, merges, original position solidification, thus forming periodic silica-based gold-nano array.
Except technique scheme, present invention also offers a kind of without enzyme hydrogen peroxide sensor, it adopts the gold-nano array electrode described in technique scheme directly as the working electrode that concentration of hydrogen peroxide is detected, it is no longer necessary to use other inertia working electrodes, this not only lowers testing cost, and simplify operating process.
Compared with prior art, gold-nano array electrode provided by the present invention at least has the advantages that
First, the gold-nano array electrode that the embodiment of the present invention provides is the gold nano grain array of the orderly six non-solid matters of side, and each gold nano grain has good monodispersity, shape subglobular.
Second, the gold-nano array electrode that the embodiment of the present invention provides, the size of its non-solid matter gold nano grain and cycle all can pass through to change parameter Effective Regulation, and this is that the detection of concentration of hydrogen peroxide in solution is provided possibility by the gold-nano array probing into different cycles.
3rd, the gold-nano array electrode that the embodiment of the present invention provides is high to the detection sensitivity of hydrogen peroxide, detection limit is low, detection range is wide, capacity of resisting disturbance is strong, good stability.
4th, concentration of hydrogen peroxide in solution directly as working electrode, can be detected by the gold-nano array electrode that the embodiment of the present invention provides, it is no longer necessary to uses other inertia working electrodes, this not only lowers testing cost, and simplify operating process.
5th, the gold-nano array electrode that the embodiment of the present invention provides only needs the conventional equipment using laboratory conventional, does not need to use special equipment, and technical process is simple to operation.
6th, the gold-nano array electrode that the embodiment of the present invention provides not only cost is low, and is appropriate to large area large-scale production, it is possible to be suitable for following industrialization large-scale application in environment, food, medical science etc..
In order to more clearly from show technical solutions according to the invention and produced technique effect, with specific embodiment, the hydrogen peroxide sensor without enzyme of gold-nano array electrode provided by the present invention and preparation thereof is described in detail below.
Embodiment 1
As it is shown in figure 1, a kind of gold-nano array electrode, following steps are adopted to be prepared from:
Step a, by microscope slide, (label 1 as described in Figure 1 is microscope slide, use as substrate of glass) it is sequentially placed in acetone, ethanol, deionized water and carries out ultrasonic cleaning, all ultrasonic cleaning 40min in every kind of liquid, again the microscope slide after cleaning is put into baking oven and carry out drying and processing, drying temperature is 70 DEG C, and drying time is 20min；After the moisture on microscope slide evaporates completely, microscope slide is positioned in UV ozone cleaning machine irradiation 30min, thus obtaining the microscope slide of surface hydrophilic.
Step b, take polystyrene colloid ball suspension (2.5wt.%) that 50 microlitre diameters are 350～1000nm, and mix with ethanol equal-volume, the sonic oscillation carrying out 10min again processes, thus preparing finely dispersed polystyrene colloid ball ethanol dilution liquid；Microscope slide 1 after being processed by step a puts into polystyrene colloid ball ethanol dilution liquid, and adopts liquid-vapor interface self-assembling method to synthesize monolayer polystyrene colloid spherocrystal volume array (label 2 as described in Figure 1 is polystyrene colloid ball) on described microscope slide.
Step c, the monolayer polystyrene colloid spherocrystal volume array of synthesis in step b is slowly tilted in immersion precursor liquid (label 3 as described in Figure 1 is precursor liquid) together with microscope slide, monolayer polystyrene colloid spherocrystal volume array is owing to being subject to liquid level surface tension effects and the overall microscope slide that departs from, and swims on precursor liquid liquid level；The monolayer polystyrene colloid spherocrystal volume array swum on precursor liquid liquid level is picked up by the silicon chip (label 4 as described in Figure 1 is silicon chip) adopting a piece of cleaning again, dry, thus can be prepared by the silica-based monolayer polystyrene colloid spherocrystal volume array of orderly monolayer.
Step d, with step c prepare silica-based monolayer polystyrene colloid spherocrystal volume array for template, employing magnetron sputtering deposition method (the process electric current of magnetron sputtering deposition is 20mA, and the process time of magnetron sputtering deposition is 3min) deposits the golden film (label 5 as described in Figure 1 is the polystyrene colloid ball that surface deposits one layer of golden film) that a layer thickness is 10～400nm on the surface of described template.
Step e, above-mentioned deposition have the template of golden film put in tube furnace, and under 900 DEG C of air atmospheres heating anneal 2 hours, single polymer layer colloidal spheres crystal array decomposes on silica-based, and the golden film on silica-based can melt, merges, original position solidification, thus preparing periodic silica-based gold-nano array (label 6 as described in Figure 1 is gold nano grain).By this silica-based gold-nano array directly as gold-nano array electrode, for concentration of hydrogen peroxide is detected.
Specifically, respectively with diameter be 350nm, 500nm, 750nm, 1000nm polystyrene colloid ball suspension for raw material, and prepare gold-nano array electrode according to the step of the invention described above embodiment 1, carry out following detection simultaneously:
(1) prepare in the process of gold-nano array electrode for raw material at the polystyrene colloid ball suspension being 350nm with diameter, adopt Sirion200 field emission scanning electron microscope that prepared silica-based monolayer polystyrene colloid spherocrystal volume array and prepared silica-based gold-nano array are observed, and shoot electron scanning micrograph (FESEM image) as shown in Figure 2；Wherein, Fig. 2 a is the low power FESEM image of the silica-based monolayer polystyrene colloid spherocrystal volume array that the polystyrene colloid ball suspension being 350nm with diameter prepares for raw material, Fig. 2 b is the high power FESEM image of the silica-based monolayer polystyrene colloid spherocrystal volume array that the polystyrene colloid ball suspension being 350nm with diameter prepares for raw material, Fig. 2 c is the low power FESEM image of the silica-based gold-nano array that the polystyrene colloid ball suspension being 350nm with diameter prepares for raw material, Fig. 2 d is the high power FESEM image of the silica-based gold-nano array that the polystyrene colloid ball suspension being 350nm with diameter prepares for raw material.By FESEM image as shown in Figure 2 it can be seen that the silica-based gold-nano array of end product has good order and monodispersity, mean diameter is 200nm, and period pitch is 350nm.
(2) prepare in the process of gold-nano array electrode for raw material at the polystyrene colloid ball suspension being 350nm with diameter, adopt PhilipsX ' Pert type x-ray diffractometer that end product (period pitch is the nano-array of 350nm) is detected, thus obtaining X-ray diffracting spectrum (XRD figure spectrum) as shown in Figure 3；Wherein, the vertical coordinate of Fig. 3 is Intensity (i.e. relative diffracted intensity), and the abscissa of Fig. 3 is 2 θ (i.e. the angles of diffraction), and unit is degree (i.e. degree).By X-ray diffracting spectrum as shown in Figure 3 it can be seen that the peak position at all X-ray diffraction peaks of end product with gold (Au:no.04-0784) standard JCPDS (JointCommitteeonPowderDiffractionStandards, JCPDS) card is consistent, and this illustrates that end product is gold nano grain.
(3) gold-nano array electrode that period pitch is 350nm that the embodiment of the present invention 1 prepares is respectively put into 0.1M (namely mole every liter) phosphate buffer (also known as PhosphateBufferedSaline or PBS buffer solution, pH value is 7.4) and 0.1M containing 5mM (namely bold and unconstrained mole every liter) hydrogen peroxide (namely mole every liter) phosphate buffer (pH value is 7.4) in, and detect the C-V characteristic of this gold-nano array electrode, thus obtaining cyclic voltammetry curve comparison diagram as shown in Figure 4；Wherein, the vertical coordinate of Fig. 4 is Current (i.e. current intensity), and unit is μ A (i.e. microampere), and the abscissa of Fig. 4 is Potential (i.e. electrode potential), and unit is V (i.e. volt).Cyclic voltammetry curve comparison diagram as shown in Figure 4 is it can be seen that when in PBS buffer solution containing hydrogen peroxide, this periodic gold-nano array electrode has significant current responsing signal.
(4) gold-nano array electrode that period pitch is 350nm that the embodiment of the present invention 1 prepares is placed in test container, and under the running voltage of 0.1V, the hydrogen peroxide of variable concentrations it is continuously added in test container, time, concentration of hydrogen peroxide and electric current are measured, thus recording the linear relationship chart of current-vs-time response curve as shown in Figure 5 and electric current as shown in Figure 6 and concentration of hydrogen peroxide simultaneously；Wherein, the vertical coordinate of Fig. 5 is Current (i.e. current intensity), unit is μ A (i.e. microampere), the abscissa of Fig. 5 is Time (i.e. the time), unit is s (i.e. the second), and the vertical coordinate of Fig. 6 is Current (i.e. current intensity), and unit is μ A (i.e. microampere), the abscissa of Fig. 6 is Concentration (i.e. concentration of hydrogen peroxide), and unit is μM (i.e. a micromole every liter).The linear relationship chart of electric current shown in current-vs-time response curve as shown in Figure 5 and Fig. 6 and concentration of hydrogen peroxide it can be seen that the gold-nano array electrode obtained by the embodiment of the present invention 1 is to the dense response having rapid sensitive of hydrogen peroxide, and current responsing signal change has very good linear relationship with concentration of hydrogen peroxide change.
(5) the prepared gold-nano array electrode that period pitch is 350nm of the embodiment of the present invention 1 current intensity at various ph values is measured, thus recording the curve chart that electric current as shown in Figure 7 changes with pH value；Wherein, the vertical coordinate of Fig. 7 is Current (i.e. current intensity), and unit is μ A (i.e. microampere), and the abscissa of Fig. 7 is pH value.The curve chart that electric current as shown in Figure 7 changes with pH value is it can be seen that the gold-nano array electrode obtained by the embodiment of the present invention 1 is respectively provided with good current-responsive within the scope of wider pH value.
(6) the prepared gold-nano array electrode that period pitch is 350nm of the embodiment of the present invention 1 current intensity at different temperatures is measured, thus recording the curve chart that electric current as shown in Figure 8 varies with temperature；Wherein, the vertical coordinate of Fig. 8 is Current (i.e. current intensity), and unit is μ A (i.e. microampere), and the abscissa of Fig. 8 is Temperature (i.e. temperature), and unit is DEG C (namely degree Celsius).The curve chart that electric current as shown in Figure 8 varies with temperature is it can be seen that the gold-nano array electrode obtained by the embodiment of the present invention 1 is respectively provided with good current-responsive in wide temperature range.
(7) gold-nano array electrode that period pitch is 350nm that the embodiment of the present invention 1 prepares is placed in test container, and under the running voltage of 0.1V, in test container, add 0.1M containing 5mM (namely bold and unconstrained mole every liter) hydrogen peroxide (namely mole every liter) phosphate buffer (pH value is 7.4), then in test container, add the interfering materials such as certain density sodium citrate, glucose, carbamide, ethanol successively；In this course, chronoamperometry is adopted to test the curent change of this gold-nano array electrode, thus recording current-vs-time response curve as shown in Figure 9；Wherein, the vertical coordinate of Fig. 9 is Current (i.e. current intensity), and unit is μ A (i.e. microampere), and the abscissa of Fig. 9 is Time (i.e. the time), and unit is s (i.e. the second)；H in Fig. 92O2Representing the addition phosphate buffer containing hydrogen peroxide, the AA in Fig. 9 represents addition sodium citrate, and the Glacose expression in Fig. 9 adds glucose, and the Urea in Fig. 9 represents addition carbamide, and the Ethanol in Fig. 9 represents addition ethanol.Current-vs-time response curve as shown in Figure 9 it can be seen that when adding sodium citrate, glucose, carbamide, ethanol in hydrogen peroxide system, there is not significant change in current-responsive, occurring almost without interference phenomenon, this illustrates that the gold-nano array electrode obtained by the embodiment of the present invention 1 has good selectivity and capacity of resisting disturbance.
(8) prepare in the process of gold-nano array electrode for raw material at the polystyrene colloid ball suspension being 500nm, 750nm, 1000nm with diameter, adopt Sirion200 field emission scanning electron microscope respectively prepared silica-based gold-nano array to be observed, and shoot electron scanning micrograph (FESEM image) as shown in Figure 10；Wherein, Figure 10 a is the high power FESEM image of the silica-based gold-nano array that the polystyrene colloid ball suspension being 500nm with diameter prepares for raw material, Figure 10 b is the high power FESEM image of the silica-based gold-nano array that the polystyrene colloid ball suspension being 750nm with diameter prepares for raw material, and Figure 10 c is the high power FESEM image of the silica-based gold-nano array that the polystyrene colloid ball suspension being 1000nm with diameter prepares for raw material.By FESEM image as shown in Figure 10 it can be seen that along with the increase of polystyrene colloid bulb diameter, the period pitch of the silica-based gold-nano array of end product also constantly increases.
(9) by be 500nm, 750nm, 1000nm with diameter polystyrene colloid ball suspension prepare gold-nano array electrode for raw material and be respectively put in 0.1M containing 5mM (i.e. person of outstanding talent mole every liter) hydrogen peroxide (namely mole every liter) phosphate buffer (pH value is 7.4), and detect the C-V characteristic of gold-nano array electrode respectively, thus obtaining cyclic voltammetry curve comparison diagram as shown in figure 11；Wherein, the vertical coordinate of Figure 11 is Current (i.e. current intensity), and unit is μ A (i.e. microampere), and the abscissa of Figure 11 is Potential (i.e. electrode potential), and unit is V (i.e. volt).Cyclic voltammetry curve comparison diagram shown in FESEM image as shown in Figure 10 and Figure 11 is it can be seen that along with the continuous of period pitch of silica-based gold-nano array increases, hydrogen peroxide electrochemical response on silica-based gold-nano array gradually reduces.As fully visible, the embodiment of the present invention not only detects low, highly sensitive, the good stability of restriction, and preparation method is simple, easy and simple to handle, with low cost, economic and environment-friendly.
The above; being only the present invention preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, any those familiar with the art is in the technical scope that the invention discloses; the change that can readily occur in or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (7)
1. a gold-nano array electrode, it is characterised in that adopt following steps to be prepared from:
Step A, prepare silica-based single polymer layer crystalline colloidal arrays, and with this silica-based single polymer layer crystalline colloidal arrays for template, adopt physical deposition method to deposit the golden film that a layer thickness is 10～400nm on the surface of described template；
Step B, above-mentioned deposition have the template of golden film thermally decompose and make annealing treatment, to remove single polymer layer crystalline colloidal arrays, thus preparing silica-based gold-nano array；By this silica-based gold-nano array directly as gold-nano array electrode.
2. gold-nano array electrode according to claim 1, it is characterised in that described silica-based single polymer layer crystalline colloidal arrays of preparing includes:
Prepare single polymer layer crystalline colloidal arrays on the glass substrate, and tilt to immerse in precursor liquid together with single polymer layer crystalline colloidal arrays by this substrate of glass；Described single polymer layer crystalline colloidal arrays departs from substrate of glass, and swims on precursor liquid liquid level；Silicon chip is adopted to be picked up by the single polymer layer crystalline colloidal arrays swum on precursor liquid liquid level again, thus preparing silica-based single polymer layer crystalline colloidal arrays.
3. gold-nano array electrode according to claim 2, it is characterised in that the described single polymer layer crystalline colloidal arrays for preparing on the glass substrate comprises the following steps:
Step A1, substrate of glass is sequentially placed in acetone, ethanol, deionized water and carries out ultrasonic cleaning, again the substrate of glass after cleaning is carried out drying and processing, it is then placed in UV ozone cleaning machine irradiation 10～40min, thus obtaining the substrate of glass of surface hydrophilic；
Step A2, step A1 is processed after substrate of glass put into polymeric colloid ball ethanol dilution liquid, and adopt liquid-vapor interface self-assembling method to synthesize single polymer layer crystalline colloidal arrays on the glass substrate.
4. gold-nano array electrode according to claim 3, it is characterized in that, described polymeric colloid ball ethanol dilution liquid adopts following methods to be prepared from: take the polymeric colloid ball suspension that polymeric colloid bulb diameter is 350～1000nm, and mix with ethanol equal-volume, the sonic oscillation carrying out 10～30min again processes, thus preparing finely dispersed polymeric colloid ball ethanol dilution liquid.
5. gold-nano array electrode according to any one of claim 1 to 4, it is characterised in that described physical deposition method includes magnetron sputtering deposition, thermal evaporation deposition or electron-beam evaporation.
6. gold-nano array electrode according to any one of claim 1 to 4, it is characterised in that described have the template of golden film to thermally decompose and make annealing treatment above-mentioned deposition to include:
The template of golden film is had to put in tube furnace above-mentioned deposition, and under 900 DEG C of air atmospheres heating anneal 2 hours, single polymer layer crystalline colloidal arrays decomposes on silica-based, and silica-based on golden film can melt, merge, original position solidification, thus forming periodic silica-based gold-nano array.
7. one kind without enzyme hydrogen peroxide sensor, it is characterised in that adopt the gold-nano array electrode according to any one of the claims 1 to 6 directly as the working electrode that concentration of hydrogen peroxide is detected.
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