CN110426439A - Wireless photoelectric chemistry indirect analysis detection device and preparation method thereof - Google Patents
Wireless photoelectric chemistry indirect analysis detection device and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of analysis and detection, disclose a kind of wireless photoelectric chemistry indirect analysis detection device and preparation method thereof, the first coordination electrode is located in the first electrolytic cell in the first electrolyte in the device, second coordination electrode is located in the second electrolytic cell in the second electrolyte, closed bipolar electrode has the optoelectronic pole of photoelectric semiconductor material to constitute by conductor, detecting electrode and load, detecting electrode and optoelectronic pole are located in the first and second electrolytic cells, first and second electrolytic cell is connected by conductor；Light source is fixed on above optoelectronic pole；First electrolyte, which includes, needs to be detected substance, contains stabilizer in the second electrolyte；Electrochemical workstation is connect by conducting wire with the first and second coordination electrodes, carries out control of Electric potentials to detecting electrode and optoelectronic pole.The present invention utilizes bipolar electrode technology for the first time, the principle based on charge conservation and carrying current, realizes the strange land detection of object.
Description
Technical field
The present invention relates to technical field of analysis and detection, in particular to a kind of wireless photoelectric chemistry indirect analysis detection device and
Its production method.
Background technique
In recent years, the analysis and testing technology based on optical electro-chemistry obtains significant progress, will be used wider and wider general.
Photoelectric analysis has the series of advantages such as equipment is simple, operation is easy, sensitivity is high.The elementary tactics of photoelectric analysis at present is logical
Cross specific wavelength light irradiation modification photoelectric activity material electrode surface, should during have electric energy, chemical energy and luminous energy it
Between mutually convert, the transfer of electronics occurs between detectable substance and photoelectric semiconductor material to generating photoelectric current, passes through photoelectricity
The size of flow valuve realizes the detection to object.As far as we know, there is presently no any technologies, can be detached from optoelectronic pole
This sensing interface realizes the detection to object.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, the present invention provides a kind of wireless photoelectric chemistry indirect analysis
Detection device and preparation method thereof, utilizes bipolar electrode technology for the first time, and the principle based on charge conservation and carrying current realizes
It detects in the strange land of object.
Technical solution: the present invention provides a kind of wireless photoelectric chemistry indirect analysis detection devices, including are located on substrate
At least one analysis detection unit, each analysis detection unit includes being located in the first electrolytic cell in the first electrolyte
The first coordination electrode, the second coordination electrode in the second electrolyte in the second electrolytic cell, closed bipolar electrode, light source
And electrochemical control system；The closed bipolar electrode has photoelectric semiconductor material by conductor, detecting electrode and load
Optoelectronic pole is constituted, and the detecting electrode is located in first electrolytic cell, and the optoelectronic pole is located in second electrolytic cell, institute
It states the first electrolytic cell and is connect with second electrolytic cell by the conductor；The light source is fixed on above the optoelectronic pole；Institute
It states containing certain density substance to be detected in the first electrolyte, second electrolyte is interior to be contained and can partly lead with the photoelectricity
The stabilizer that body material is had an effect；The electrochemical workstation passes through conducting wire and first coordination electrode and the second control electricity
Pole connection carries out control of Electric potentials to the detecting electrode and optoelectronic pole.
Preferably, the indirect analysis detection device is composed in parallel by at least described analysis detection unit.
Preferably, the photoelectric semiconductor material is anode photoelectric semiconductor material or cathode luminous semiconductor material.Light
Electric semiconductor material is carried on optoelectronic pole, can be loaded by common such as Electrostatic Absorption, Van der Waals force, chemical bonding means
On optoelectronic pole, photoelectric semiconductor material can be all kinds of common semiconductor materials such as inorganic, organic, under specific wavelength irradiation
Forbidden band is broken through to generate photohole and form photovoltage.It is preferred that photoelectric semiconductor material is cadmiumsulfide quantum dot.
Preferably, first electrolytic cell and second electrolytic cell are to be affixed on structure on the substrate by cyclic annular dielectric
At electrolytic cell.First electrolytic cell and the second electrolytic cell can be common electrolytic cell, or be pasted by cyclic annular dielectric
In two electrolytic cells constituted on substrate.
Preferably, first coordination electrode and second coordination electrode are unpolarized electrode, preferably silver/silver chlorate
Electrode.The purpose of first coordination electrode and the second coordination electrode is to maintain relatively stable current potential, so that electrochemical control system
The current potential that the detecting electrode and optoelectronic pole on closed bipolar electrode are mainly controlled when adjusting current potential excludes the dry of other factors
It disturbs.
Preferably, the detecting electrode and optoelectronic pole are made of indium tin oxide, gold, platinum or conductive carbon material.
Preferably, the light source is the light that can excite any wavelength of the photoelectric semiconductor material generation photoelectric current
Source.Light source is capable of providing the energy for breaking through photoelectric semiconductor material forbidden band depending on photoelectric semiconductor material, and optimal wavelength is
The ultraviolet light of 410 nm.
Preferably, the stabilizer is redox for that can generate with the photoelectric semiconductor material under illumination condition
Electroactive material, preferably ascorbic acid.Stabilizer obtains or loses electronics under the effect of specific photovoltage, partly leads with photoelectricity
Directly the have an effect value of theoretical photoelectric current of generation of body material is much larger than the oxidation that generates on detecting electrode of substance to be detected
Reduction current.
Preferably, first electrolyte and second electrolyte are the buffer solution for being capable of providing ionic current, excellent
Select PBS buffer solution.
The present invention also provides a kind of production methods of wireless photoelectric chemistry indirect analysis detection device, including following step
It is rapid: S1: to print out the first control electricity of each analysis detection unit on the substrate using electrically conductive ink and silk-screen template
Pole, the second coordination electrode and its external connection and closed bipolar electrode；S2: use cover plate by first electrolytic cell and institute
The area covers for stating the second electrolytic cell cover other regions using wax seal technology, form two independent first electricity
Second electrolytic cell described in Xie Chihe；S3: by photoelectric semiconductor material drop coating in the photoelectricity pole surface, the fixed institute of fixative is used
State photoelectric semiconductor material；S4: described is connected respectively to by the working electrode of the electrochemical control system, to reference electrode
In one coordination electrode and second coordination electrode；S5: the first electrolyte containing substance to be detected is instilled described the
In one electrolytic cell, the second electrolyte containing stabilizer is added in second electrolytic cell；S6: the electrochemical control is used
System controls the current potential of first coordination electrode and second coordination electrode, so that entire analysis and detection device exists
With lower and stable base current when there is no illumination；S7: the optoelectronic pole, note are irradiated using light source every preset time period
The corresponding curent change of the optoelectronic pole is recorded, realizes the Photoelectric Detection to the substance to be detected.
Working principle: under conditions of specific light source irradiation, photoelectric material generates photohole and forms specific photoelectricity
Pressure, stabilizer are oxidated or reduced as electron donor or receptor, generate the transfer of electronics；Substance to be detected is on detecting electrode
It is reduced or aoxidizes.It should be pointed out that the redox current that substance to be detected generates is much smaller than photoelectric material and stabilization
Agent reacts the photoelectric current of generation, and the electric current of such whole system is mainly by the redox of substance to be detected on detecting electrode
Electric current is controlled, that is to say, that based on the conservation between detecting electrode and optoelectronic pole there is charge, what substance to be detected generated
Redox current will limit the photoelectric current of photoelectric material and stabilizer generation, and the degree of limitation and the concentration of substance to be detected have
Light obtains the relationship between the concentration of substance to be detected and photoelectric current size in this way, to realize to be detected
The indirect detection of substance.
The utility model has the advantages that compared with prior art, the present invention having following obvious advantage:
One, in wireless photoelectric chemistry indirect analysis detection device of the invention, detecting electrode is with optoelectronic pole with extraneous not by leading
Line is directly connected to, and the conduction of charge only occurs by electrolyte, is a kind of wireless sensing modes；Do not connected by direct conducting wire
Connect can be realized on optoelectronic pole chemistry and bio-sensing, can be used for many conventional photo analysis methods be not available it is specific
Place.
Two, wireless photoelectric chemistry indirect analysis detection device of the invention is a kind of novel photoelectronic analyzer, to be checked
It surveys substance and traditional detection Photoelectric Detection is different, need not be present on the electrode surface where optoelectronic pole and partly led with photoelectricity
Body material is had an effect, it can be achieved that the strange land to test object is detected.
As long as the three, test object of wireless photoelectric chemistry indirect analysis detection device of the invention theoretically electric active matter
Matter all can realize indirect Photoelectric Detection by way of charge conservation, greatly expand the range of Photoelectric Detection.
Four, wireless photoelectric chemistry indirect analysis detection device of the invention, not only can detecte directly on detecting electrode
Redox electroactive material occurs, can also be realized by constructing all kinds of chemistry and bio-sensing mechanism to all kinds of no electricity
The Photoelectric Detection of chemically reactive substance.
Five, the present invention have the characteristics that preparation cost it is low, it is widely used, facilitate it is convenient.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of wireless photoelectric chemistry indirect analysis detection device in the present invention；
Fig. 2 is the photocurrent response figure of the hydrogen peroxide of various concentration when 0.1 V using CdS as photoelectric material.
Wherein, 1 it is substrate, 2 be the first electrolytic cell, 3 be the first coordination electrode, 4 be the second electrolytic cell, 5 is the second control
Electrode, 6 be light source, 7 be electrochemical control system, 8 be conductor, 9 be detecting electrode, 10 be photoelectric semiconductor material, 11 be light
Electrode, 12 are conducting wire.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
The present invention provides a kind of wireless photoelectric chemistry indirect analysis detection devices, as shown in Figure 1, including one is located at base
Analysis detection unit on piece 1, the analysis detection unit is mainly by the first electrolytic cell 2, the second electrolytic cell 4, the first coordination electrode
3, the second coordination electrode 5, closed bipolar electrode, light source 6 and electrochemical control system 7 form, closed bipolar electrode by
Conductor 8, detecting electrode 9 and load have the optoelectronic pole 11 of photoelectric semiconductor material 10 to constitute, and detecting electrode 9 is located at the first electrolytic cell
In 2, optoelectronic pole 11 is located in the second electrolytic cell 4, and the first electrolytic cell 2 is connect with the second electrolytic cell 4 by conductor 8, and light source 6 is fixed
Above optoelectronic pole 11.There is the first electrolyte containing certain density substance to be detected, the first control in first electrolytic cell 2
Electrode 3 is located in the first electrolyte in the first electrolytic cell 2, has in the second electrolytic cell 4 containing can be with optoelectronic semiconductor material
Second electrolyte of the stabilizer that material 10 is had an effect, the second coordination electrode 5 are located at the second electrolyte in the second electrolytic cell 4
It is interior；Electrochemical control system 7 is connect by conducting wire 12 with the first coordination electrode 3 and the second coordination electrode 5, to 9 He of detecting electrode
Optoelectronic pole 11 carries out control of Electric potentials, using to electrochemical control system 7 be required to the size of record current value.
Above-mentioned wireless photoelectric chemistry indirect analysis detection device the production method is as follows (to construct paper base Integral wireless light
For electrochemistry indirect analysis detection device, use cadmium sulfide as photoelectric semiconductor material, ascorbic acid as stabilizer,
PBS buffer solution is as the first electrolyte and the second electrolyte, and hydrogen peroxide is as substance to be detected, as shown in Fig. 1):
(1) specific silk-screen template is customized, prints out the control of the first coordination electrode 3, second on paper base substrate 1 using electrically conductive ink
Electrode 5 and its external connection processed and closed bipolar electrode after drying, modify 3 He of the first coordination electrode using Ag/AgCl elargol
Second coordination electrode 5.
(2) easy cover plate is constructed to cover 4 area covers of the first electrolytic cell 2 and the second electrolytic cell using wax seal technology
Other regions are covered, two independent first electrolytic cells 2 and the second electrolytic cell 4 are formed.
(3) cadmiumsulfide quantum dot (oneself can synthesize also can purchase) drop coating on the surface of optoelectronic pole 11, is used into chitosan
Fixed cadmiumsulfide quantum dot.
(4) by the working electrode of electrochemical control system 7, the first coordination electrode 3 and second is coupled with to reference electrode
In coordination electrode 5.
(5) substance to be detected will be contained --- the PBS buffer solution of hydrogen peroxide instills in the first electrolytic cell 2, will contain
The PBS buffer solution of stabilizer --- ascorbic acid is added in the second electrolytic cell 4, and ascorbic acid needs higher as stabilizer
Concentration is set as 100 mM herein.
(6) current potential of electrochemical control system 7 is arranged in 0 V or so, the micro-tensioning system by way of instant electric current
Current potential, so that whole system is in no illumination with lower and stable base current.
(7) optoelectronic pole 11 is irradiated using the ultraviolet source 6 that wavelength is 410 nm, it is primary every 20 s irradiation, when irradiation
A length of 20 s records the corresponding curent change of entire analysis and detection device, as shown in Fig. 2, its stepped ramp type photoelectric current is to correspond to
The corresponding photocurrent values of hydrogen peroxide under various concentration.The corresponding photocurrent values of various concentration hydrogen peroxide are recorded, and to corresponding
Data analyzed, it can realize to the Photoelectric Detection of hydrogen peroxide.
By Fig. 2 as it can be seen that being coated with cadmiumsulfide quantum dot on optoelectronic pole 11, the anti-of 100 mM is added in the second electrolytic cell 4
The PBS buffer solution containing various concentration hydrogen peroxide is added in bad hematic acid in the first electrolytic cell 2, under the conditions of 0.1 V, uses
410 nm light source 6(600 W) at interval of a 20 S optoelectronic pole 11 of irradiation, to generate the step-flow of different height, step
The height of electric current can react the height of concentration of hydrogen peroxide indirectly.
The working principle of above-mentioned wireless photoelectric chemistry indirect analysis detection device is as follows: in the ultraviolet source 6 of 410 nm
Under conditions of irradiation, the cadmiumsulfide quantum dot on optoelectronic pole 11 generates photohole and forms specific photovoltage, and stabilizer is made
It is oxidated or reduced for electron donor or receptor, generates the transfer of electronics；Substance to be detected be reduced on detecting electrode 9 or
Oxidation.It should be pointed out that the redox current that substance to be detected generates is sent out much smaller than cadmiumsulfide quantum dot and ascorbic acid
The photoelectric current that raw reaction generates, the electric current of such whole system is mainly by the redox electricity of substance to be detected on detecting electrode 9
Stream is controlled, that is to say, that based on the conservation between detecting electrode 9 and optoelectronic pole 11 there is charge, substance to be detected is generated
Redox current will limit the photoelectric current that cadmiumsulfide quantum dot and ascorbic acid generate, the degree of limitation and substance to be detected
Concentration have light, in this way, the relationship between the concentration of substance to be detected and photoelectric current size is obtained, to realize
Treat the indirect detection of detection substance.
The technical concepts and features of above embodiment only to illustrate the invention, its object is to allow be familiar with technique
People cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent transformation or modification that Spirit Essence is done, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of wireless photoelectric chemistry indirect analysis detection device, it is characterised in that: including at least one being located on substrate (1)
Analysis detection unit, each analysis detection unit include first in the first electrolyte in the first electrolytic cell (2)
Coordination electrode (3), the second coordination electrode (5) in the second electrolyte in the second electrolytic cell (4), closed bipolar electrode,
Light source (6) and electrochemical control system (7)；The closed bipolar electrode is had by conductor (8), detecting electrode (9) and load
The optoelectronic pole (11) of photoelectric semiconductor material (10) is constituted, and the detecting electrode (9) is located in first electrolytic cell (2), institute
It states optoelectronic pole (11) to be located in second electrolytic cell (4), first electrolytic cell (2) passes through with second electrolytic cell (4)
Conductor (8) connection；The light source (6) is fixed on above the optoelectronic pole (11)；Containing certain in first electrolyte
The substance to be detected of concentration, second electrolyte are interior steady containing that can have an effect with the photoelectric semiconductor material (10)
Determine agent；The electrochemical control system (7) passes through conducting wire (12) and first coordination electrode (3) and the second coordination electrode (5)
Connection carries out control of Electric potentials to the detecting electrode (9) and optoelectronic pole (11).
2. wireless photoelectric chemistry indirect analysis detection device according to claim 1, which is characterized in that the indirect analysis
Detection device is composed in parallel by at least described analysis detection unit.
3. wireless photoelectric chemistry indirect analysis detection device according to claim 1, which is characterized in that the photoelectricity is partly led
Body material (10) is anode photoelectric semiconductor material or cathode luminous semiconductor material.
4. wireless photoelectric chemistry indirect analysis detection device according to claim 1, which is characterized in that first electrolysis
Pond (2) and second electrolytic cell (4) are to be affixed on the electrolytic cell constituted on the substrate (1) by cyclic annular dielectric.
5. wireless photoelectric chemistry indirect analysis detection device according to claim 1, which is characterized in that first control
Electrode (3) and second coordination electrode (5) are unpolarized electrode.
6. wireless photoelectric chemistry indirect analysis detection device according to any one of claim 1 to 5, which is characterized in that
The detecting electrode (9) and optoelectronic pole (11) are made of indium tin oxide, gold, platinum or conductive carbon material.
7. wireless photoelectric chemistry indirect analysis detection device according to any one of claim 1 to 5, which is characterized in that
The light source (6) is the light source that can excite any wavelength of the photoelectric semiconductor material generation photoelectric current.
8. wireless photoelectric chemistry indirect analysis detection device according to any one of claim 1 to 5, which is characterized in that
The stabilizer is that can generate redox electroactive material with the photoelectric semiconductor material under illumination condition.
9. wireless photoelectric chemistry indirect analysis detection device according to any one of claim 1 to 5, first electrolysis
Matter and second electrolyte are the buffer solution for being capable of providing ionic current.
10. a kind of production side of wireless photoelectric chemistry indirect analysis detection device as claimed in any one of claims 1-9 wherein
Method, which comprises the following steps:
S1: the first control of each analysis detection unit is printed out on the substrate (1) using electrically conductive ink and silk-screen template
Electrode (3), the second coordination electrode (5) and its external connection processed and closed bipolar electrode；
S2: using cover plate by the area covers of first electrolytic cell (2) and second electrolytic cell (4), wax seal skill is used
Art covers other regions, forms two independent first electrolytic cells (2) and second electrolytic cell (4)；
S3: by photoelectric semiconductor material (10) drop coating on the optoelectronic pole (11) surface, the fixed photoelectricity half of fixative is used
Conductor material (10)；
S4: by the working electrode of the electrochemical control system (7), first coordination electrode is connected respectively to reference electrode
(3) and in second coordination electrode (5)；
S5: the first electrolyte containing substance to be detected is instilled in first electrolytic cell (2), by second containing stabilizer
Electrolyte is added in second electrolytic cell (4)；
S6: using the electrochemical control system (7) to first coordination electrode (3) and second coordination electrode (5)
Current potential is controlled, so that entire analysis and detection device is in no illumination with lower and stable base current；
S7: the optoelectronic pole (11) is irradiated using light source (6) every preset time period, it is corresponding to record entire analysis and detection device
Curent change realizes the Photoelectric Detection to the substance to be detected.
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