CN106770187A - A kind of electrochromic devices array and its preparation, application method - Google Patents
A kind of electrochromic devices array and its preparation, application method Download PDFInfo
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Abstract
The invention discloses a kind of electrochromic devices array and preparation method thereof, and this sensor array is successfully applied to lactate detection.The sensor array includes multiple sensors, each sensor includes battery compartment and transducing part respectively, transducing part includes sensing electrode and example reaction pond, Prussia's Bluepoint is modified with the working electrode of sensing electrode, the cathodic reaction zone and anode reaction area in example reaction pond are respectively comprising the substrate and detection reagent being made up of paper, detection reagent in cathodic reaction zone is the cushioning liquid containing LO, and the detection reagent in anode reaction area is the cushioning liquid containing the potassium ferricyanide.During lactate detection, according to the difference of lactic acid concn to be measured, indicate the number of lattice array discoloration different.Can indicate the number that point changes colour by naked eye to judge the concentration of lactic acid.The sensor array is prepared simply, easy to use, without detecting circuit, reaction result can be directly observed by naked eyes, with good application value.
Description
Technical field
The invention belongs to Electrochemical Detection analysis field, more particularly to a kind of electrochromic devices based on open hole detection
Array and preparation method thereof, and for the half-quantitative detection of lactic acid.
Background technology
2007, the Whiteside seminars of Harvard University proposed the concept in paper chip laboratory first, i.e., it is biological,
The elementary cells such as chemistry, the sample preparation of medical analysis process, reaction, separation, detection are integrated on paper and complete.Due to paper chip
Laboratory has low cost, preparation method simple (using simple printing technique, and without harsh conditions such as dust free rooms), operation
Simply (without additional equipment, such as pump), using it is rear disposable the advantages of, get more and more people's extensive concerning.
At present, the analysis method set up on paper chip technology platform is broadly divided into two classes, and a class is method for qualitative analysis
Such as colorimetric method, this kind of method can only provide the signal response of " Yes/No ", and colorimetric method sensitivity is relatively low, and selectivity is poor；It is another
Class is quantitative analysis method such as electrochemical assay, is that bio signal is converted into electric signal by redox reaction, this kind of
Method detection sensitivity is high, fast response time, however it is necessary that special detecting instrument carries out the detection of result, increased detection
Complexity and cost, and have impact on the portability of paper chip.
The content of the invention
Goal of the invention：The present invention applies the problem of presence for current refill chip technology in analysis method, there is provided a kind of
The electrochromic devices array that sensitivity is high, selectivity is good, with low cost, easy to use, the electrochromic devices array
Lactate detection can be successfully applied to.Meanwhile, the method the invention provides preparing and use the electrochromic devices array.Should
Sensor array combines the advantage of qualitative detection and quantitative determination, prepares simply, easy to use, without detecting circuit, can lead to
Naked eyes directly observation reaction result is crossed, with good application value.
Technical scheme：To achieve these goals, one aspect of the present invention provides a kind of electrochromic devices battle array
Row, it includes multiple sensors, and each sensor includes battery compartment and transducing part respectively；Transducing part includes sensing electrode
With example reaction pond；Sensing electrode includes working electrode and reference electrode, and Prussia's Bluepoint is modified with working electrode；Sample is anti-
Ying Chi includes cathodic reaction zone and anode reaction area, and cathodic reaction zone and anode reaction area are made up of and by Nafion paper respectively
Film separates, and detection reagent is respectively provided with the cathodic reaction zone and anode reaction area, the detection examination in the cathodic reaction zone
Agent is the cushioning liquid containing LO, and the detection reagent in the anode reaction area is that the buffering containing the potassium ferricyanide is molten
Liquid.
Because ito thin film has high conductivity, electrode material is suitable as, and be easy to observation, bendable with high light transmittance
Bent sexual compatibility is combined with paper sensor, at the same it is with low cost, therefore sensing electrode selects ito thin film electrode.
For reduces cost, electrochromism response sensitivity is improved, the detection reagent for making cathodic reaction zone is to contain 250U
The 0.01M PBSs of LO, pH 7.4, the detection reagent for making anode reaction area is to contain 500mM iron cyanogen
Change the 0.01M PBSs of potassium, pH 7.4.
In order to improve the integrated level of sensing chip, the present invention directly integrates battery with transducing part.Based on paper
Metal-oxygen battery much study, the present invention selection aluminium as metal material, make alumina battery, its output voltage is in 1V
Left and right, is adapted to the demand of follow-up sensing detection, and aluminium is with low cost, is easy to obtain.The positive pole of alumina battery uses printing-ink,
Its positive pole is with reference electrode in the conductive side with a piece of ito thin film；The negative pole of alumina battery uses aluminum foil material, its negative pole and institute
Working electrode is stated in the conductive side with a piece of ito thin film；Positive pole and negative pole are separated by paper.
Another aspect of the present invention provides a kind of preparation method of electrochromic devices array, and it includes following step
Suddenly：
1) two rectangle ito thin films are respectively cut into pectination；Take a cleaved ito thin film, using comb portion as
Reference electrode, the comb handle portion coating cell positive material that comb portion one end is connected with each other forms positive pole；Take another cleaved
Ito thin film, comb portion as working electrode, and by comb portion one end be connected with each other comb handle portion covering cell negative electrode material make
It is negative pole；
2) conductive side in working electrode modifies Prussia's Bluepoint；
3) be cascading cathodic reaction zone, Nafion membrane and anode reaction area, intermediate layer is formed, by the intermediate layer
Be set to the working electrode and reference electrode identical shape, form example reaction pond, the intermediate layer is arranged on work
Between electrode and reference electrode, the cathodic reaction zone overlaps with the working electrode, the anode reaction area with it is described
Reference electrode overlaps；
4) separated by paper between positive pole and negative pole, paper shape is more than positive pole and negative pole；
5) cushioning liquid containing LO is added dropwise in cathodic reaction zone, normal temperature lucifuge is dried in the shade；In anode reaction area
The cushioning liquid containing the potassium ferricyanide is added dropwise, normal temperature lucifuge is dried in the shade；
6) lactic acid solution of normal concentration gradient is taken, step 5 is sucked successively) example reaction of sensor array that obtains
Pond, normal temperature dries in the shade, and forms preset solution area；
7) lactic acid solution of different concentration knowns being taken, respectively with step 6) formation that obtains has the sensor in preset solution area
Array is detected that obtain the corresponding relation of lactic acid solution concentration to be measured and Prussia's Bluepoint discoloration, the difference is known
The lactic acid solution concentration of concentration is respectively 0,4,8,12,16,20mM.
For reduces cost, electrochromism response sensitivity is improved, Prussia's Bluepoint is modified using electro-deposition method
Working electrode surface；The deposition liquid pH for using electro-deposition is 2.0, deposition liquid comprising 10mM iron chloride, the 10mM potassium ferricyanides and
2.6mM hydrochloric acid.
In below 2mM, sweat lactic acid concn can reach human sweat's lactic acid concn after a large amount of motions under normal circumstances
20mM, in order that lactate detection scope is in 0~20mM, and combines the number of sensor in sensor array, by lactate detection
Discrimination is set to 4mM, therefore makes step 6) concentration gradient be 0,4,8,12,16,20mM.
An additional aspect of the present invention provides a kind of application method of electrochromic devices array,
1) draw saturated nacl aqueous solution and enter the battery compartment, turn on battery plus-negative plate；
2) lactic acid solution to be measured is taken into the example reaction pond, makes to proceed by redox in example reaction pond anti-
Should；
3) after reaction a period of time, the color change of Prussia's Bluepoint is observed, the number of the Prussia's Bluepoint according to discoloration
Would know that the concentration of lactic acid solution to be measured.
Beneficial effect：The electrochromic devices array that the present invention is provided, bio signal is converted into bore hole can directly know
Other color change is used for half-quantitative detection, and detection process is simple and quick, without professional's operation, without outside energy supply, nothing
Need additional detection apparatus, chip is easily prepared, can volume production prepare, it is cheap and with good practicality.Related in the present invention
And the electrochromic devices array based on open hole detection method of production compared with prior art have advantages below：
1st, prepare simply, it is cheap；
2nd, easy to operate, suitable layman uses；
3rd, without externally fed, sensor array carries alumina battery, easy to use；
4th, without additional detections device, bore hole Direct Recognition carries out half-quantitative detection；
5th, detect quick：Detection time was controlled within 1 minute, disclosure satisfy that the demand of Site Detection.
Brief description of the drawings
Fig. 1 is each layer cross-sectional view of sensor of the invention array；
It is Prussian blue when Fig. 2A -2C are the lactic acid solution of sensor array detection various concentrations to form preset solution area
The discoloration schematic diagram of point；Wherein, Fig. 2A is the overall schematic of sensor array when not adding lactic acid solution to be measured, Fig. 2 B
For add 10mM lactic acid solutions when sensor array in Prussia's Bluepoint discoloration schematic diagram, Fig. 2 C for add 1mM lactic acid
During solution in sensor array Prussia's Bluepoint discoloration schematic diagram；
Fig. 3 adds the result figure of Prussia's Bluepoint discoloration in sensor array for the lactic acid solution to be measured of various concentrations；
Fig. 4 is the corresponding relation curve of lactic acid solution concentration and the number of Prussia's Bluepoint discoloration.
Fig. 5 is to carry out test result to the repeatability of sensor of the invention array with 6mM lactic acid solutions.
1st, working electrode；2nd, reference electrode；3rd, Prussia's Bluepoint；4th, anode；5th, GND；6th, cell partition
Paper；7th, cathodic reaction zone；8th, Nafion membrane；9th, anode reaction area；10th, preset solution area.
Specific embodiment
The present invention is described in further details below in conjunction with the accompanying drawings.
Embodiment 1 is based on the electrochromic devices array of open hole detection
A kind of electrochromic devices array based on open hole detection, is made up of 6 sensors, and each sensor is included
Two parts：Battery compartment and transducing part.
As shown in figure 1, transducing part includes ITO electrode and example reaction pond.ITO electrode includes working electrode 1 and reference
Electrode 2, they all use ito thin film material, Prussia's Bluepoint 3 are wherein modified with working electrode as indicator.Prussia
The diameter of Bluepoint 3 is 1.12mm, and using electro-deposition method modification on the surface of working electrode 1, the deposition liquid that deposition process is used is
60 μ L solution, pH 2.0, the solution includes 10mM iron chloride, the 10mM potassium ferricyanides and 2.6mM hydrochloric acid.Example reaction pond includes
Cathodic reaction zone 7 and anode reaction area 9, and cathodic reaction zone 7 and anode reaction area 9 substrate by paper constitute, cathode reaction
Area 7 and anode reaction area 9 are separated by Nafion membrane 8.
The reagent of addition is 5 μ L 0.01M PBS solutions in advance in cathodic reaction zone 7, and pH 7.4 contains in the solution
250U LOs；The reagent of addition is 5 μ L 0.01M PBS solutions, pH 7.4, in the solution in advance in anode reaction area
Contain the 500mM potassium ferricyanides.
Battery compartment is constituted using alumina battery, and wherein positive pole 4 uses printing-ink, the positive pole 4 to exist with reference electrode 2
With the conductive side of a piece of ito thin film；Negative pole 5 uses aluminum foil material, and the negative pole 5 is with working electrode 1 with a piece of ito thin film
Conductive side.Positive pole and negative pole are separated by paper 6.
Embodiment 2 is based on the preparation of the electrochromic devices array of open hole detection
Electrochromic devices array based on open hole detection provided by the present invention, its preparation process includes following step
Suddenly：
A) with laser cutting machine two rectangle ito thin films are cut out as in Fig. 1 corresponding shape as sensor array
Substrate, i.e. cut to ito thin film along the direction parallel with the first side of rectangle ito thin film respectively, made and first side
The second vertical side is separated from each other to form 6 stripes, is connected with each other at the parallel the 3rd with described second, so as to form comb
Shape structure；
A cleaved ito thin film is taken, using comb portion as reference electrode 2, the comb that comb portion one end is connected with each other
Shank coats the rectangular ink of 2mm × 15mm and dries in the shade, and forms anode 4；Another cleaved ito thin film is taken, is combed
The comb handle portion that comb portion one end is connected with each other is sticked the aluminium with the same shape of anode 4 as working electrode 1 for teeth portion
Paper tinsel, forms GND 5；
B) working electrode 1 a diameter of 1.12mm of conductive side electro-deposition Prussian blue round dot 3, detailed process is：
B-1) configuration concentration is the ferric chloride solution of 100mM, concentration for the potassium ferricyanide solution and concentration of 500mM are 1M's
Hydrochloric acid solution；
B-2 100 μ L ferric chloride solutions, 20 μ L potassium ferricyanide solutions, 880 μ L ultra-pure waters) are taken to be well mixed, will with watery hydrochloric acid
PH is adjusted to 2.0, and this mixed solution is used as deposition liquid；
B-3 double faced adhesive tape) is cut off circular hole of a diameter of 1.12mm as mask with laser cutting machine, working electrode is covered in
1 fixed position；
B-4 two electrode systems) are formed with working electrode 1 as reference electrode with platinum filament, 60 μ L is taken and is deposited liquid as electrolysis
Liquid, Prussian blue electro-deposition is carried out using galvanostatic method, and setting cathode current is 1E-6A, and sedimentation time is 60s；
B-5 double faced adhesive tape mask) is removed, is cleaned up liquid is deposited with ultra-pure water, working electrode 1 puts dry.
C) be cascading cathodic reaction zone 7 (paper substrates), Nafion membrane 8 and anode reaction area 9 (paper substrates),
Intermediate layer is formed, intermediate layer is cut out into the size same with cathodic reaction zone 7 and anode reaction area 9, form example reaction pond, its
Middle cathodic reaction zone 7 overlaps with working electrode 1, and anode reaction area 9 overlaps with reference electrode 2, working electrode 1 and ginseng
Than electrode 2 conductive side to inner close fitting intermediate layer.
D) stick paper 6 between positive pole 4 and negative pole 5 to separate, the shape of paper is slightly larger than positive pole 4 and negative pole 5.
E) in 5 μ L of the dropwise addition of cathodic reaction zone 7, the LO solution that concentration is 250U, 5 μ L of the dropwise addition of anode reaction area 9,
Concentration is the potassium ferricyanide solution of 500mM, and normal temperature lucifuge is dried in the shade.
F) lactic acid solution for taking 3 μ L normal concentration gradients sucks the example reaction pond of sensor array successively, and normal temperature dries in the shade,
Preset solution area is formed, the concentration gradient is 0,4,8,12,16,20mM；
G) lactic acid solution of different concentration knowns is taken, the sensor array obtained with step f) is detected respectively, is obtained
The corresponding relation of lactic acid solution concentration to be measured and Prussia's Bluepoint discoloration.
Overall chip apparatus figure is as shown in Figure 2.The negative pole of alumina battery is aluminium foil, and positive pole is carbon ink material, and centre is used
Used as electrolytic cell, when electrolyte is sucked in paper, there is alumina reaction in battery conducting to paper, produce the voltage of 1V or so to supply core
Piece sensing response is used.The operation principle of transducing part is that, when lactic acid solution is sucked, lactic acid is in the presence of LO
The potassium ferricyanide is reduced into potassium ferrocyanide；It is Prussian blue to form redox couple with potassium ferrocyanide, in battery powered feelings
Under condition, electronics is obtained from battery and is reduced into colourless Prussia in vain, while potassium ferrocyanide is oxidized.Its reaction equation
It is as follows：
Negative electrode：PB+e-→PW
It is Prussian blue be reduced required for electronics to be oxidized the electron number for losing with potassium ferrocyanide equal, then with breast
The concentration of acid is related.By controlling the process of Prussian blue electro-deposition, enable Prussian blue complete when lactic acid concn is 20mM
The full Prussia that is reduced into becomes colorless in vain, i.e., the Prussian blue test limit for becoming colorless completely is 20mM.By in sensing
The lactic acid of preset various concentrations gradient in device, you can different numbers in making sensor array in the case of the various concentrations lactic acid to be measured
The sensor of amount reaches Prussian blue test limit, the Prussian blue of varying number then occurs and becomes colorless, and visually observes knot
Really.
During specific detection, during suction various concentrations lactic acid solution to be measured, the Prussia's Bluepoint in sensor array is by blueness
The number for becoming colorless is different, can observe by the naked eye the number of Prussia's Bluepoint so as to learn the concentration of lactic acid to be measured.If dense
Degree parameter C is equal to preset lactic acid concn and lactic acid sample concentration sum to be measured.When concentration parameter C is not less than 20mM, Pu Lu
Scholar's indigo plant becomes colorless completely.
Fig. 2A is to add the lactic acid solution of normal concentration gradient to form preset solution area only in sensor array, is not added
The overall schematic of sensor array during lactic acid solution to be measured, although now there is a preset breast of sensor in sensor array
Acid solutions reach 20mM, because the preset lactic acid solution of 20mM in Fig. 2A is that preset lactic acid is drawn into sensor base,
Do not contacted with Prussian blue (PB), do not reacted, therefore without the discoloration of Prussia's Bluepoint.Fig. 2 B are addition 10mM lactic acid
During solution in sensor array Prussia's Bluepoint discoloration schematic diagram, now have 3 Prussia's Bluepoints in sensor array
Become colorless.Fig. 2 C are the discoloration schematic diagram of Prussia's Bluepoint in sensor array when adding 1mM lactic acid solutions, are now passed
There is 1 Prussia's Bluepoint to become colorless in sensor array.
As shown in figure 3, when lactic acid solution concentration to be measured is less than 4mM, concentration parameter C is not less than 20mM in sensor array
Only one of which, therefore the Prussian blue number for becoming colorless be 1.The lactic acid of 0~20mM can be entered according to the method
Row half-quantitative detection, the resolution ratio of detection is 4mM.
Lactic acid concn is as shown in Figure 4 with the number relation curve of Prussia's Bluepoint bleach.
Embodiment 3 is based on the electrochromic devices array detection lactic acid of open hole detection：
Electrochromic devices array based on open hole detection in embodiment 1 is used to detect lactic acid, is comprised the steps of：
1) saturated nacl aqueous solution is configured, turns in the paper 6 of the solution inspiration battery compartment, alumina battery.
2) negative pole of alumina battery is aluminium foil, and positive pole is carbon ink material, centre paper as electrolytic cell, when being inhaled in paper
When entering electrolyte, there is alumina reaction in battery conducting, produce the voltage of 1V or so to be used for sensing chip reaction.Transducing part
Operation principle be, when suck lactic acid solution when, the potassium ferricyanide is reduced into ferrous cyanogen by lactic acid in the presence of LO
Change potassium；It is Prussian blue to form redox couple with potassium ferrocyanide, in the case of battery powered, electronics quilt is obtained from battery
Colourless Prussia is reduced into white, while potassium ferrocyanide is oxidized.It is Prussian blue to be reduced required electronics with ferrous cyanogen
Change potassium and be oxidized that the electron number for losing is equal, then the concentration to lactic acid is related.By controlling the process of Prussian blue electro-deposition,
The Prussian blue Prussia that is reduced into completely when lactic acid concn is for 20mM is become colorless in vain, i.e., it is Prussian blue complete
The test limit for becoming colorless is 20mM.By the lactic acid of preset various concentrations gradient in the sensor, you can treated in various concentrations
The sensor of varying number in sensor array is reached Prussian blue test limit in the case of surveying lactic acid, then occur different
The Prussian blue of quantity becomes colorless, visual results.During specific detection, 18 μ L lactic acid solutions to be measured are drawn anti-into sample
Ying Chi, starts timing, and example reaction proceeds by redox reaction in pond.
3) after reaction 30s, the color for observing Prussia's Bluepoint of sensor array whether there is, according to the Prussian blue of bleach
The number of point can directly know the concentration of lactic acid solution to be measured.
The repeatability of this sensor array is tested with 6mM lactic acid, as shown in Figure 5.Where each row it is Prussian blue
Dot matrix is a testing result for sensor array, as can be seen that the Pu Lu for becoming colorless from five results of retest
The quantity of scholar's Bluepoint is all 2, and the repeatability of this sensor array is preferably.
Claims (10)
1. a kind of electrochromic devices array, it is characterised in that the sensor array includes multiple sensors, each sensing
Device includes battery compartment and transducing part respectively；The transducing part includes sensing electrode and example reaction pond；The sensing electricity
Pole includes working electrode (1) and reference electrode (2), and Prussia's Bluepoint (3) is modified with the working electrode (1)；The sample
Reaction tank includes cathodic reaction zone (7) and anode reaction area (9), the cathodic reaction zone (7) and anode reaction area (9) respectively by
Paper is constituted and separated by Nafion membrane (8), and detection examination is respectively provided with the cathodic reaction zone (7) and anode reaction area (9)
Agent, the detection reagent in the cathodic reaction zone (7) is the cushioning liquid containing LO, the anode reaction area (9)
In detection reagent be the cushioning liquid containing the potassium ferricyanide.
2. electrochromic devices array according to claim 1, it is characterised in that the working electrode (1) and reference
Electrode (2) uses ito thin film electrode.
3. electrochromic devices array according to claim 1, it is characterised in that described slow containing LO
It is the 0.01M PBSs containing 250U LOs to rush solution, and pH is in the range of 7.0~7.5.
4. electrochromic devices array according to claim 1, it is characterised in that the buffering containing the potassium ferricyanide
Solution is the 0.01M PBSs containing the 500mM potassium ferricyanides, and pH is in the range of 7.0~7.5.
5. electrochromic devices array according to claim 1, it is characterised in that the battery is alumina battery, institute
The positive pole (4) for stating alumina battery uses printing-ink, and the positive pole (4) is with the reference electrode (2) with a piece of ito thin film
Conductive side；The negative pole (5) of the alumina battery uses aluminum foil material, and the negative pole (5) is with the working electrode (1) with a piece of
The conductive side of ito thin film；The positive pole (4) and negative pole (5) are separated by paper (6).
6. the preparation method of the electrochromic devices array described in any one of Claims 1 to 5, it is characterised in that including with
Lower step：
1) two ito thin films are respectively cut into pectination；A cleaved ito thin film is taken, using comb portion as reference electrode
(2) the comb handle portion coating cell positive material that, comb portion one end is connected with each other forms positive pole (4)；Take another cleaved
Ito thin film, comb portion is made as working electrode (1), the comb handle portion covering cell negative electrode material that comb portion one end is connected with each other
It is negative pole (5)；
2) conductive side in working electrode (1) modifies Prussia's Bluepoint (3)；
3) be cascading cathodic reaction zone (7), Nafion membrane (8) and anode reaction area (9), intermediate layer is formed, by centre
Layer be set to the working electrode (1) and reference electrode (2) identical shape, formation example reaction pond, the intermediate layer sets
Put between working electrode (1) and reference electrode (2), the cathodic reaction zone (7) overlaps with the working electrode (1),
The anode reaction area (9) overlaps with the reference electrode (2)；
4) separated by paper (6) between the positive pole (4) and the negative pole (5), paper (6) shape is more than positive pole (4) and bears
Pole (5)；
5) cushioning liquid containing LO is added dropwise in cathodic reaction zone (7), normal temperature lucifuge is dried in the shade；In anode reaction area
(9) cushioning liquid containing the potassium ferricyanide is added dropwise, normal temperature lucifuge is dried in the shade；
6) lactic acid solution of normal concentration gradient is taken, step 5 is sucked successively) the example reaction pond of sensor array that obtains, often
Temperature is dried in the shade, and forms preset solution area；
7) lactic acid solution of different concentration knowns being taken, with step 6) sensor array that obtains detected respectively, obtains lactic acid
The corresponding relation of solution concentration and Prussia's Bluepoint discoloration, the lactic acid solution concentration of the different concentration knowns is respectively 0,
4,8,12,16,20mM.
7. the preparation method of electrochromic devices array according to claim 6, it is characterised in that described Prussian blue
Point is using electro-deposition method modification in working electrode surface.
8. the preparation method of electrochromic devices array according to claim 6, it is characterised in that the electro-deposition is adopted
Deposition liquid pH is 2.0, and the deposition liquid includes 10mM iron chloride, the 10mM potassium ferricyanides and 2.6mM hydrochloric acid.
9. the preparation method of electrochromic devices array according to claim 6, it is characterised in that step 6) in, institute
It is 0,4,8,12,16,20mM to state normal concentration gradient.
10. the application method of the electrochromic devices array according to any one in claim 1-5, its feature exists
In：
1) draw saturated nacl aqueous solution and enter the battery compartment, turn on battery plus-negative plate；
2) lactic acid solution to be measured into the example reaction pond is taken, makes to proceed by redox reaction in example reaction pond；
3) after reaction a period of time, the color change of Prussia's Bluepoint is observed, the number of the Prussia's Bluepoint according to discoloration
Would know that the concentration of lactic acid solution to be measured.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111381412A (en) * | 2020-04-01 | 2020-07-07 | 宁波祢若电子科技有限公司 | Complementary electrochromic device and preparation method thereof |
| CN111812082A (en) * | 2020-07-01 | 2020-10-23 | 淮阴工学院 | Photoelectrochemistry electrochromism indirect analysis and detection device and manufacturing method thereof |
| CN115236148A (en) * | 2022-07-19 | 2022-10-25 | 中国科学院烟台海岸带研究所 | Salinity detection sensor suitable for coastal zone sediment environment and detection method thereof |
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| CN115236148B (en) * | 2022-07-19 | 2023-12-22 | 中国科学院烟台海岸带研究所 | Salinity detection sensor suitable for coastal zone sediment environment and detection method thereof |
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