CN104391017B - A kind of sensor and preparation method thereof - Google Patents
A kind of sensor and preparation method thereof Download PDFInfo
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- CN104391017B CN104391017B CN201410410774.1A CN201410410774A CN104391017B CN 104391017 B CN104391017 B CN 104391017B CN 201410410774 A CN201410410774 A CN 201410410774A CN 104391017 B CN104391017 B CN 104391017B
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Abstract
The present invention relates to a kind of sensor, this sensor includes electrode cores and has the conductive polymer membrane of three-dimensional ordered macroporous structure, and described conductive polymer membrane is attached on the surface of described electrode cores.The preparation method that the invention still further relates to a kind of sensor, and relate to sensor prepared by the method.The present invention forms the sensor of the conductive polymer membrane with three-dimensional ordered macroporous structure by preparing on the surface of electrode cores, improve sensor detection hydroquinone time stability and repeatability, and its detection limit is low, it is possible in wider scope, hydroquinone is detected, highly sensitive.
Description
Technical field
The present invention relates to a kind of sensor, the preparation method of a kind of sensor, and sensor prepared by the method.
Background technology
At present, the detection of aldehydes matter mainly adopts the technological means such as chromatograph, color-matter coupling, it is necessary to use large complicated instrument and equipment, and energy consumption is high, and analysis time is long, is difficult to carry out scene, quickly detect, and is unfavorable for town and country popularity.Different, electrochemical sensor possesses sensitive, quick, low energy consumption, low cost, easily automatically controls, is suitable for the features such as field assay, thus enjoys favor, applies increasingly extensive.Aldehydes matter all contains electroactive group (phenolic hydroxyl group), can produce redox current by receiving and losing electrons under certain potentials, and this provides theoretical basis for electrochemical gaging aldehydes matter.But from current research conditions, the preparation method of these nano electrochemical sensors is nearly all first synthesize nano-particle, then it is dispersed in specific solvent, take proper amount of nano particle dispersion drop coating to electrode surface, after solvent flashing, nanoparticle is fixed on electrode surface by physical actions such as hydrophobic, absorption and forms nano thin-film.There is many defects in the nano electrochemical sensor of detection aldehydes matter prepared by this dispersion drop-coating.First: sensitivity is very low, and analysis time is long.Reason is mainly and is, aldehydes matter electro-chemical activity on general sensor is poor, the signal of telecommunication produced is faint, for making up the deficiency of transducer sensitivity, all adopts long-time enrichment to improve aldehydes matter in the concentration of sensor surface and response signal during practical measurement；Second: nano-particle and electrode surface in conjunction with weak, poor stability, service life is short；3rd: adopting manual dropping, uniformity of film is difficult to ensure that, and is subject to ambient temperature, humidity, and the isoparametric impact of solvent polarity, volatility has a strong impact on the repeatability of its measurement result.Therefore, how to be obtained in that the aldehydes matter nano sensitive material that stability height, favorable reproducibility, performance are more excellent is to be badly in need of solution, challenging research topic at present at electrode surface.
In recent years, There-dimensional ordered macroporous materials (3DOM) receives much concern, There-dimensional ordered macroporous materials not only has the general characteristic of usual porous material, as specific surface area is big, the character such as porosity is high, but also it is periodically strong to have pore structure arrangement, pore-size distribution is narrow, the a series of own characteristic such as hole dimension is uniformly adjustable and overall structure three-dimensional long-range is orderly, the hole wall of macropore is generally made up of nanoparticle, the characteristic of nanometer particle material and orderly macroporous structure are combined, be conducive to producing novel function or characteristic, also make There-dimensional ordered macroporous materials in new catalyst or catalyst carrier, the aspects such as electrode material have good application potential.At present, have been reported that and poly L-cysteine is used for preparing sensor, but owing to poly L-cysteine is non-conductive, so depositional coating can not be too thick, the advantage causing There-dimensional ordered macroporous materials can not embody completely, additionally, the stability of poly L-cysteine modified electrode is also bad.
Therefore, a kind of stability height, favorable reproducibility, the nano-sensor detecting aldehydes matter that performance is more excellent now it are badly in need of.
Summary of the invention
It is an object of the invention to overcome the stability of the nano-sensor detecting aldehydes matter in prior art low and poor reproducibility, the defect that sensor performance is poor, it is provided that a kind of sensor, the preparation method of a kind of sensor, and sensor prepared by the method.
The present inventor finds under study for action, as long as sensor includes electrode cores and has the conductive polymer membrane of three-dimensional ordered macroporous structure, and described conductive polymer membrane is attached on the surface of described electrode cores.Stability when can improve sensor for detecting phenol, repeatability and sensitivity, and improve the performance of sensor.
Therefore, to achieve these goals, the invention provides a kind of sensor, this sensor includes electrode cores and has the conductive polymer membrane of three-dimensional ordered macroporous structure, and described conductive polymer membrane is attached on the surface of described electrode cores.
On the other hand, the preparation method that present invention also offers a kind of sensor, the method includes:
(1) on the surface of electrode cores, by the method for acceleration vertical deposition, microsphere is self-assembled into colloidal crystal template；
(2) by the cyclic voltammetry gap filled conductive polymer at colloidal crystal template；
(3) by the solvent dissolving removal colloidal crystal template of described colloidal crystal template can be dissolved.
The third aspect, present invention also offers sensor prepared by method as above.
The present invention forms the sensor of the conductive polymer membrane with three-dimensional ordered macroporous structure by preparing on the surface of electrode cores, improve sensor detection hydroquinone time stability and repeatability, and its detection limit is low, it is possible in wider scope, hydroquinone is detected, highly sensitive.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Fig. 1 is a kind of colloidal crystal template of the present invention；
Fig. 2 is a kind of conductive polymer membrane with three-dimensional ordered macroporous structure of the present invention；
Fig. 3 is the cyclic voltammogram of the poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles of embodiments of the invention 1 electro-deposition；
Fig. 4 is the DPV response diagram that hydroquinone carries out DPV test on the sensor that embodiment 1-6 and comparative example 1 prepare；
Fig. 5 is hydroquinone to be continuously performed DPV in the sensors A 1 that embodiment 1 prepares and tests the DPV response diagram of 20 times；
Fig. 6 is hydroquinone to be continuously performed DPV on the sensor D1 that comparative example 1 prepares and tests the DPV response diagram of 20 times；
Fig. 7 is the DPV response diagram that the hydroquinone of variable concentrations carries out the different hydroquinone concentration of DPV test in the sensors A 1 that embodiment 1 prepares；
Fig. 8 is the working curve according to Fig. 7 size of current drawn with hydroquinone concentration.
Detailed description of the invention
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The invention provides a kind of sensor, this sensor includes electrode cores and has the conductive polymer membrane (as shown in Figure 2) of three-dimensional ordered macroporous structure, and described conductive polymer membrane is attached on the surface of described electrode cores.
In the present invention, three-dimensional ordered macroporous structure refers to that the size of macropore is single, and pore structure is at the loose structure of three dimensions ordered arrangement.
According to sensor of the present invention, wherein, as long as sensor includes electrode cores and has the conductive polymer membrane of three-dimensional ordered macroporous structure, and described conductive polymer membrane is attached on the surface of described electrode cores, stability when can improve sensor for detecting phenol, repeatability and sensitivity, to improve the performance of sensor.But stability during in order to improve sensor further for detecting phenol, repeatability and sensitivity, to improve the performance of sensor, it is preferable that the material of conductive polymer membrane is selected from poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles, poly-3 methyl thiophene and poly-2,5-dimercapto-1,3, at least one in 4-thiadiazoles, it is more preferably poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
According to sensor of the present invention, wherein, three-dimensional ordered macroporous structure can be the three-dimensional ordered macroporous structure of the nanometer-scale of this area routine, preferably, in three-dimensional ordered macroporous structure, the aperture of macropore is 300-350nm, stability when can improve sensor further for detecting phenol, repeatability and sensitivity, thus improving the performance of sensor, more preferably 305-325nm.In the present invention, in three-dimensional ordered macroporous structure, the aperture of macropore is defined as the diameter in hole, and this aperture adopts scanning electron microscope to be measured.
According to sensor of the present invention, wherein, the thickness of conductive polymer membrane can be the thickness that can play electric action that this area is conventional, preferably, the thickness of conductive polymer membrane is 80-150nm, it is possible to improves sensor further and is used for sensitivity when detecting phenol and reduces detection limit, thus improving the performance of sensor, being more preferably 90-110nm, in the present invention, the thickness of conductive polymer membrane adopts scanning electron microscope to be measured.
According to sensor of the present invention, wherein, in sensor, electrode cores can be the electrode cores of this area routine, for instance can be the one in glass-carbon electrode core, gold electrode core and copper electrode core, it is preferred to glass-carbon electrode core.
On the other hand, the preparation method that present invention also offers a kind of sensor, the method includes:
(1) on the surface of electrode cores, by the method for acceleration vertical deposition, microsphere is self-assembled into colloidal crystal template；
(2) by the cyclic voltammetry gap filled conductive polymer at colloidal crystal template；
(3) by the solvent dissolving removal colloidal crystal template of described colloidal crystal template can be dissolved.
In the present invention, it should be appreciated by those skilled in the art, electrode cores is column, and the surface of electrode cores refers to the part that electrode is exposed.
According to method of the present invention, wherein, as long as microsphere being self-assembled into colloidal crystal template (as shown in Figure 1) by accelerating the method for vertical precipitation on the surface of electrode cores, then pass through the cyclic voltammetry gap filled conductive polymer at colloidal crystal template, finally dissolve with solvent and remove colloidal crystal template, can be prepared by during detection phenol stability and favorable reproducibility, highly sensitive, and the sensor of excellent performance.nullBut in order to improve prepared sensor further for detecting stability during phenol、Repeatability and sensitivity，To improve the performance of sensor，Preferably，The preparation method of this sensor also includes: front in step (1)，The surface of electrode cores is carried out pretreatment，The method of this pretreatment can be: first polish the surface of electrode cores with aluminium oxide，Then electrode cores surface is completely infused in the mixed solution being mixed to get with NaOH solution and hydrogen peroxide and carries out ultrasonic Treatment 10-12 minute，Hyperacoustic power is 80-160W，Electrode cores surface is completely infused in successively the aqueous solution of nitric acid of 50-60 volume % again、Dehydrated alcohol、Deionized water proceeds ultrasonic Treatment 3-5 minute，Finally dry up standby with nitrogen，Wherein，The concentration of NaOH solution is 5-10mol/L，The concentration of hydrogen peroxide is 25-35 volume %，The volume ratio of NaOH solution and hydrogen peroxide is 1:1-2.
According to method of the present invention, wherein, as long as the film that conducting polymer prepares ensure that conduct electricity, preferably, conducting polymer is selected from poly-2-amino-5-sulfydryl-1, and 3,4-thiadiazoles, poly-3 methyl thiophene and poly-2,5-dimercapto-1,3, at least one in 4-thiadiazoles, it is more preferably poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles, it is thus possible to stability when improving further the sensor for preparing for detecting phenol, repeatability and sensitivity, to improve the performance of sensor.
According to method of the present invention, wherein, in step (1), the method accelerating vertical deposition can be the method for this area routine, such as may include that in the above-mentioned electrode cores thorough impregnation through pretreatment to the polystyrene aqueous solution that mass fraction is 0.1%, then this solution is put in the baking oven of 55-60 DEG C, take out after 2-3 days, namely obtain colloidal crystal template.Wherein polystyrene can prepare and can also be purchased.
What it should be appreciated by those skilled in the art is, the detailed process of cyclic voltammetry can be the operating process of the cyclic voltammetry of this area routine, can think: adopt containing conducting polymer monomer and sulfur aqueous acid, in electrochemical workstation, conducting polymer electro-deposition is filled into the gap of colloidal crystal template.
According to method of the present invention, wherein, in step (2), the condition of described cyclic voltammetry can be the condition of conventional cyclic voltammetry, preferably, this condition includes: the concentration of conducting polymer monomer is 0.1-3mmol/L, the concentration of sulphuric acid is 1-20mmol/L, and the mol ratio of conducting polymer and sulphuric acid is 1:0.3-20, when the number of turns of deposition is 30-60, sensitivity when can improve prepared sensor further for detecting phenol also reduces detection limit, thus improving the performance of sensor.When this preferred cyclic voltammetry, it is possible to the thickness making the conductive polymer membrane prepared is 80-150nm.
More preferably, the condition of described cyclic voltammetry includes: the concentration of conducting polymer monomer is 0.8-1.2mmol/L, the concentration of sulphuric acid is 8-12mmol/L, and the mol ratio of conducting polymer and sulphuric acid is 1:10-13, when the number of turns of deposition is 40-45, sensitivity when can improve prepared sensor further for detecting phenol also reduces detection limit, thus improving the performance of sensor.When this preferred cyclic voltammetry, it is possible to the thickness making the conductive polymer membrane prepared is 90-110nm.
In the preferred embodiment of the present invention, cyclic voltammetry condition also includes: sweep limits is-0.35-2V, sweeps speed for 100mV/s.
In the present invention, the diameter of microsphere can be the size that this area is conventional, for instance the diameter that can control microsphere is 250-400nm, within the scope of this microsphere diameter, it is possible to making the aperture of macropore in the final three-dimensional ordered macroporous structure prepared is 305-325nm.
According to method of the present invention, wherein, as long as the kind of microsphere ensure that can be self-assembled into colloidal crystal template in step (1), for instance can be at least one in polystyrene microsphere, silicon dioxide and polymethyl methacrylate.
In the present invention, it is possible to the solvent dissolving described colloidal crystal template can be at least one in toluene, ethyl phenyl ether and Fluohydric acid..When microsphere is polystyrene microsphere, solvent is toluene, and when microsphere is silicon dioxide, solvent is Fluohydric acid., and when microsphere is polymethyl methacrylate, solvent is ethyl phenyl ether.
According to sensor of the present invention, wherein, in sensor, electrode cores can be electrode cores as above, does not repeat them here.
The third aspect, present invention also offers sensor prepared by method as above.
Embodiment
In the following Examples and Comparative Examples, 2-amino-5-sulfydryl-1,3,4-thiadiazoles are purchased from Shanghai traditional Chinese medicines group, and the trade mark is Shanghai examination；Glass-carbon electrode is purchased from profound scholar Rui Lian company, and the diameter of electrode cores is 3mm.
In the following Examples and Comparative Examples, in the thickness of film and three-dimensional ordered macroporous structure, the aperture of macropore all adopts scanning electron microscope (Electronic Speculum company of Japan, JSM-6510LV) to measure.
The preparation method of polystyrene is: by styrene decompression distillation, it is 10% sodium hydroxide solution and deionized water wash 10 times with mass fraction respectively, obtain the styrene that purity is higher, 8.1249g styrene (purity is 99.5%) and 150mL deionized water are added in three-necked bottle, at N270 DEG C of heated at constant temperature in atmosphere, are subsequently adding 0.2075g initiator potassium persulfate, constant speed stirring 12h, can obtain milky polystyrene microemulsion, this emulsion deionized water be made into the polystyrene aqueous solution that mass fraction is 0.1% standby.
Embodiment 1
The present embodiment is used for sensor of the invention and preparation method thereof is described
(1) surface of glass-carbon electrode core is first polished with aluminium oxide, then the surface of electrode cores is completely infused in the mixed solution that the hydrogen peroxide of the NaOH solution with 7mol/L and 30 volume % is mixed to get according to the ratio of volume ratio 1:1 and carries out ultrasonic Treatment 10 minutes, hyperacoustic power is 80W, again the surface of electrode cores is completely infused in the aqueous solution of nitric acid of 50 volume %, dehydrated alcohol and deionized water successively and proceeds ultrasonic Treatment 3 minutes, hyperacoustic power is still 80W, finally dries up standby with nitrogen.Then by the electrode cores thorough impregnation of pretreatment to the polystyrene aqueous solution of 0.1%, then this solution is put in the baking oven of 55 DEG C, take out after 2 days, obtain the colloidal crystal template that polystyrene microsphere diameter is 350nm.
(2) in electrochemical workstation, adopt 2-amino-5-sulfydryl-1,3,4-thiadiazoles and sulfur aqueous acid, fill poly-2-amino-5-sulfydryl-1 by cyclic voltammetry in the gap electro-deposition of colloidal crystal template, 3,4-thiadiazoles, wherein, in cyclic voltammetry, sweep limits is-0.35-2V, sweep speed for 100mV/s, 2-amino-5-sulfydryl-1,3, the concentration of 4-thiadiazoles is 1.2mmol/L, the concentration of sulphuric acid is 10mmol/L, and 2-amino-5-sulfydryl-1,3, the mol ratio of 4-thiadiazoles and sulphuric acid is 1:9, and the number of turns of deposition was 45 (as shown in Figure 3)；
(3) filling is reunited 2-amino-5-sulfydryl-1,3, the glass-carbon electrode of 4-thiadiazoles is fully immersed in toluene 24 hours, to be completely dissolved removal colloidal crystal template, now, on the surface of this glass-carbon electrode core, just define the poly-2-amino-5-sulfydryl-1 with three-dimensional ordered macroporous structure, 3,4-thiadiazoles film, has prepared sensors A 1, and the area of electrode cores is 0.07cm2；
(4) measuring to obtain poly-2-amino-5-sulfydryl-1 on sensors A 1 surface respectively, the thickness of 3,4-thiadiazoles films is 110nm, and in three-dimensional ordered macroporous structure, the aperture of macropore is 325nm.
Embodiment 2
The present embodiment is used for sensor of the invention and preparation method thereof is described
(1) surface of glass-carbon electrode core is first polished with aluminium oxide, then the surface of electrode cores is completely infused in and carries out ultrasonic Treatment 11 minutes in the mixed solution being mixed to get according to the ratio of volume ratio 1:2 with the NaOH solution of 10mol/L and the hydrogen peroxide of 35 volume %, hyperacoustic power is 120W, again the surface of electrode cores is completely infused in the aqueous solution of nitric acid of 50 volume %, dehydrated alcohol and deionized water successively and proceeds ultrasonic Treatment 3 minutes, hyperacoustic power is 130W, finally dries up standby with nitrogen.Then will, in the electrode cores thorough impregnation of pretreatment to the polystyrene aqueous solution of 0.1%, this solution be put in the baking oven of 60 DEG C, take out after 3 days, obtain the colloidal crystal template that polystyrene microsphere diameter is 300nm.
(2) in electrochemical workstation, adopt 2-amino-5-sulfydryl-1,3,4-thiadiazoles and sulfur aqueous acid, fill poly-2-amino-5-sulfydryl-1 by cyclic voltammetry in the gap electro-deposition of colloidal crystal template, 3,4-thiadiazoles, wherein, in cyclic voltammetry, sweep limits is-0.35-2V, sweep speed for 100mV, 2-amino-5-sulfydryl-1,3, the concentration of 4-thiadiazoles is 1mmol/L, the concentration of sulphuric acid is 8mmol/L, and 2-amino-5-sulfydryl-1,3, the mol ratio of 4-thiadiazoles and sulphuric acid is 1:10, and the number of turns of deposition is 42；
(3) filling is reunited 2-amino-5-sulfydryl-1,3, the glass-carbon electrode of 4-thiadiazoles is fully immersed in toluene 24 hours, to be completely dissolved removal colloidal crystal template, now, on the surface of this glass-carbon electrode core, just define the poly-2-amino-5-sulfydryl-1 with three-dimensional ordered macroporous structure, 3,4-thiadiazoles film, has prepared sensors A 2, and the area of electrode cores is 0.07cm2；
(4) measuring to obtain poly-2-amino-5-sulfydryl-1 on sensors A 2 surface respectively, the thickness of 3,4-thiadiazoles films is 100nm, and in three-dimensional ordered macroporous structure, the aperture of macropore is 316nm.
Embodiment 3
The present embodiment is used for sensor of the invention and preparation method thereof is described
(1) surface of glass-carbon electrode core is first polished with aluminium oxide, then the surface of electrode cores is completely infused in and carries out ultrasonic Treatment 11 minutes in the mixed solution being mixed to get according to the ratio of volume ratio 1:2 with the NaOH solution of 10mol/L and the hydrogen peroxide of 35 volume %, hyperacoustic power is 160W, again the surface of electrode cores is completely infused in the aqueous solution of nitric acid of 50 volume %, dehydrated alcohol and deionized water successively and proceeds ultrasonic Treatment 3 minutes, hyperacoustic power is 160W, finally dries up standby with nitrogen.Then will, in the electrode cores thorough impregnation of pretreatment to the polystyrene aqueous solution of 0.1%, this solution be put in the baking oven of 60 DEG C, take out after 3 days, obtain the colloidal crystal template that polystyrene microsphere diameter is 280nm.
(2) in electrochemical workstation, adopt 2-amino-5-sulfydryl-1,3,4-thiadiazoles and sulfur aqueous acid, fill poly-2-amino-5-sulfydryl-1 by cyclic voltammetry in the gap electro-deposition of colloidal crystal template, 3,4-thiadiazoles, wherein, in cyclic voltammetry, sweep limits is-0.35-2V, sweep speed for 100mV, 2-amino-5-sulfydryl-1,3, the concentration of 4-thiadiazoles is 0.8mmol/L, the concentration of sulphuric acid is 10mmol/L, and 2-amino-5-sulfydryl-1,3, the mol ratio of 4-thiadiazoles and sulphuric acid is 1:12, and the number of turns of deposition is 40；
(3) filling is reunited 2-amino-5-sulfydryl-1,3, the glass-carbon electrode of 4-thiadiazoles is fully immersed in toluene 24 hours, to be completely dissolved removal colloidal crystal template, now, on the surface of this glass-carbon electrode core, just define the poly-2-amino-5-sulfydryl-1 with three-dimensional ordered macroporous structure, 3,4-thiadiazoles film, has prepared sensors A 3, and the area of electrode cores is 0.07cm2；
(4) measuring to obtain poly-2-amino-5-sulfydryl-1 on sensors A 3 surface respectively, the thickness of 3,4-thiadiazoles films is 90nm, and in three-dimensional ordered macroporous structure, the aperture of macropore is 305nm.
Embodiment 4
The present embodiment is used for sensor of the invention and preparation method thereof is described
Sensor is prepared according to the method for embodiment 1, the difference is that, by 2-amino-5-sulfydryl-1,3,4-thiadiazoles replace with 3 methyl thiophene, prepare sensors A 4.
Embodiment 5
The present embodiment is used for sensor of the invention and preparation method thereof is described
Sensor is prepared according to the method for embodiment 1, the difference is that, the polystyrene microsphere that diameter is 350nm is replaced with the polystyrene microsphere that diameter is 500nm, in the three-dimensional ordered macroporous structure of formation, the aperture of macropore is 500nm, prepares sensors A 5.
Embodiment 6
The present embodiment is used for sensor of the invention and preparation method thereof is described
Sensor is prepared according to the method for embodiment 1, the difference is that, in step (2), in cyclic voltammetry, 2-amino-5-sulfydryl-1,3, the concentration of 4-thiadiazoles is 2mmol/L, and the concentration of sulphuric acid is 20mmol/L, and 2-amino-5-sulfydryl-1, the mol ratio of 3,4-thiadiazoles and sulphuric acid is 1:15, and the number of turns of deposition is 50, the poly-2-amino-5-sulfydryl-1 formed, the thickness of 3,4-thiadiazoles films is 150nm, prepares sensors A 6.
Comparative example 1
The poly-2-amino-5-sulfydryl-1 of first synthesis, 3,4-thiadiazoles nano-particle, preparation method is: join in reaction unit by 16g sodium hydroxide, 12g hydration amine (volume fraction is 50%), 75mL deionized water, 0.25g tetrabutylammonium chloride, stirring, reagent dissolves transparent solution；It is slowly added to Carbon bisulfide 61g under cooling condition (10 DEG C), slowly it is heated to 45 DEG C and starts backflow, when heating to 100 DEG C of nothing backflow drops, reaction reaches completely, it is subsequently cooled to room temperature (25 DEG C), dropping concentrated hydrochloric acid (mass fraction is 37%) acidifying, namely having white solid to precipitate out, filtrate is yellow.Filtrate being filtered, the solid matter being filtrated to get is crude product, by this crude product 40 DEG C of use after dry 24 hours in vacuum drying oven, then at room temperature carries out recrystallization with dehydrated alcohol, namely prepares poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles nano-particle；The poly-2-amino-5-sulfydryl-1 that 0.5g is prepared, 3, the mixing of 4-thiadiazoles nano-particle, 50mg conductive agent acetylene black is dissolved in 0.5gN-methyl pyrrolidone (solvent), taking this mixture appropriate and be coated onto electrode surface, after solvent flashing, nanoparticle is fixed in glassy carbon electrode surface by hydrophobic, adsorption, form nano thin-film, this thin film is not three-dimensional ordered macroporous structure, and thickness is identical with embodiment 1, prepares sensor D1.
Test case
Test case 1
Respectively on the sensor D1 that the embodiment 1-6 sensors A 1-A6 prepared and comparative example 1 prepare, hydroquinone being carried out DPV test, the condition of DPV test is: interval time 0.3s, amplitude 0.09s, modulate time 0.1s, test result is shown in Fig. 4.
Continuously performing DPV on the sensor D1 that the sensors A prepared in embodiment 1 by hydroquinone respectively and comparative example 1 prepare to test 20 times, DPV test condition is: interval time 0.3s, amplitude 0.09s, the modulation time is 0.1s, and test result is shown in Fig. 5, Fig. 6 respectively.
The hydroquinone of variable concentrations is carried out DPV test in the sensors A 1 that embodiment 1 prepares, DPV test condition be: interval time 0.3s, amplitude 0.09s, modulation time 0.1s, obtain the DPV response diagram (as shown in Figure 7) of different hydroquinone concentration, and the working curve (as shown in Figure 8) of size of current and hydroquinone concentration is set up according to this DPV response diagram, working curve is linear respectively in the scope of 0.5-100 μM and 100-500 μM, its regression equation is respectively, I (μ A)=0.13C (μM)+0.037, I (μ A)=0.084C (μM)+6.14.
Adopt and measure with the aforedescribed process, record the hydroquinone of the variable concentrations DPV response diagram on sensor prepared by embodiment 2-6 and comparative example 1 and corresponding working curve (not shown), the slope of working curve is calculated by working curve, and utilizing equation below meter sensitivity, result of calculation is in Table 1.
Measuring the embodiment 1 prepared sensors A 1 detection limit to hydroquinone, measure the sensor of embodiment 2-6 and comparative example 1 detection limit to hydroquinone according to identical assay method, testing result is in Table 1.
The assay method of detection limit is: 3 times of the standard deviation of n blank experiment value divided by sensitivity.
Table 1
As seen in Figure 4, hydroquinone peak current of DPV response on sensors A 1-A3 is higher than on sensor D1 and A4-A6, illustrates that hydroquinone is had good electrochemical response by the sensor that the present invention prepares；Fig. 5 is hydroquinone to be continuously performed DPV in the sensors A 1 that embodiment 1 prepares and tests the DPV response diagram of 20 times, Fig. 6 is hydroquinone to be continuously performed DPV on the sensor D1 that comparative example 1 prepares and tests the DPV response diagram of 20 times, can be seen that by comparing, after the sensor METHOD FOR CONTINUOUS DETERMINATION that the present invention prepares 20 times, peak current is basically unchanged, and the stability of sensor is better；Being can be seen that by table 1 detection of the sensors A 1-A3 detection hydroquinone of embodiment 1-3 is limited to 0.3-0.4 μM/L (S/N=3), sensitivity is 0.53-88.4AM-1cm-2, the range of linearity is 0.5-500 μM, and these parameters compare with sensors A 4-A6 and D1, illustrates that hydroquinone can be detected by the sensor that the present invention prepares in wider scope, and sensitivity is higher, and detection range is wider.
Therefore, the present invention forms the sensor of the conductive polymer membrane with three-dimensional ordered macroporous structure by preparing on the surface of electrode cores, improve sensor detection hydroquinone time stability and repeatability, and its detection limit is low, in wider scope, hydroquinone can be detected, highly sensitive.
The present invention completes under the support of state natural sciences fund (Nos.21361009,21175033) and Hubei Province's Natural Science Fund In The Light (No.2012FFC02401).
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing; but; the present invention is not limited to the detail in above-mentioned embodiment; in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (18)
1. a sensor, it is characterized in that, this sensor includes electrode cores and has the conductive polymer membrane of three-dimensional ordered macroporous structure, and described conductive polymer membrane is attached on the surface of described electrode cores, and in described three-dimensional ordered macroporous structure, the aperture of macropore is 300-350nm.
2. sensor according to claim 1, wherein, the material of the described conductive polymer membrane at least one selected from poly-2-amino-5-sulfydryl-1, in 3,4-thiadiazoles, poly-3 methyl thiophene and poly-2,5-dimercapto-1,3,4-thiadiazoles.
3. sensor according to claim 2, wherein, the material of described conductive polymer membrane is poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
4. the sensor according to any one in claim 1-3, wherein, in described three-dimensional ordered macroporous structure, the aperture of macropore is 305-325nm.
5. the sensor according to any one in claim 1-3, wherein, the thickness of described conductive polymer membrane is 80-150nm.
6. sensor according to claim 5, wherein, the thickness of described conductive polymer membrane is 90-110nm.
7. the sensor according to any one in claim 1-3, wherein, described electrode cores is the one in glass-carbon electrode core, gold electrode core and copper electrode core.
8. sensor according to claim 7, wherein, described electrode cores is glass-carbon electrode core.
9. the preparation method of a sensor, it is characterised in that the method includes:
(1) on the surface of electrode cores, by the method for acceleration vertical deposition, microsphere is self-assembled into colloidal crystal template；
(2) by the cyclic voltammetry gap filled conductive polymer at colloidal crystal template；
(3) by the solvent dissolving removal colloidal crystal template of described colloidal crystal template can be dissolved；
Described sensor includes electrode cores and has the conductive polymer membrane of three-dimensional ordered macroporous structure, and in described three-dimensional ordered macroporous structure, the aperture of macropore is 300-350nm.
null10. method according to claim 9，Wherein，The method also includes: front in step (1)，The surface of electrode cores is carried out pretreatment，The method of this pretreatment includes: first polish the surface of electrode cores with aluminium oxide，Then electrode cores surface is completely infused in the mixed solution being mixed to get with NaOH solution and hydrogen peroxide and carries out ultrasonic Treatment 10-12 minute，Hyperacoustic power is 80-160W，Electrode cores surface is completely infused in successively the aqueous solution of nitric acid of 50-60 volume % again、Dehydrated alcohol、Deionized water proceeds ultrasonic Treatment 3-5 minute，Finally dry up standby with nitrogen，Wherein，The concentration of NaOH solution is 5-10mol/L，The concentration of hydrogen peroxide is 25-35 volume %，The volume ratio of NaOH solution and hydrogen peroxide is 1:1-2.
11. method according to claim 9, wherein, the described conducting polymer at least one selected from poly-2-amino-5-sulfydryl-1, in 3,4-thiadiazoles, poly-3 methyl thiophene and poly-2,5-dimercapto-1,3,4-thiadiazoles.
12. method according to claim 11, wherein, described conducting polymer is poly-2-amino-5-sulfydryl-1,3,4-thiadiazoles.
13. the method according to any one in claim 9-12, wherein, in step (2), the condition of described cyclic voltammetry includes: the concentration of conducting polymer monomer is 0.1-3mmol/L, the concentration of sulphuric acid is 1-20mmol/L, and the mol ratio of conducting polymer monomer and sulphuric acid is 1:0.3-20, the number of turns of deposition is 30-60.
14. method according to claim 13, wherein, the condition of described cyclic voltammetry includes: the concentration of conducting polymer monomer is 0.8-1.2mmol/L, and the concentration of sulphuric acid is 8-12mmol/L, and the mol ratio of conducting polymer monomer and sulphuric acid is 1:9-13, the number of turns of deposition is 40-45.
15. according to the method described in any one in claim 9-12, wherein, described microsphere at least one in polystyrene microsphere, silicon dioxide and polymethyl methacrylate.
16. according to the method described in any one in claim 9-12, wherein, described electrode cores is the one in glass-carbon electrode core, gold electrode core and copper electrode core.
17. method according to claim 16, wherein, described electrode cores is glass-carbon electrode core.
18. sensor prepared by the method according to any one in claim 9-17.
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