CN108007993A - A kind of photoelectricity pH sensors and preparation method thereof - Google Patents
A kind of photoelectricity pH sensors and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to sensor technical field, discloses a kind of photoelectricity pH sensors and preparation method thereof, and the photoelectricity pH sensors include：Shell with first chamber and second chamber.First chamber is sealed chamber, and display module, one-chip computer module, signal processing module and field-effect transistor are arranged in first chamber；PH electrodes include platinum electrode and the sensitive electrode being set in the platinum electrode, the middle part of second chamber inner top is fixed in one end of platinum electrode and sensitive electrode, and sensitive electrode is the titanium tube of inner surface and outer surface carried titanium dioxide nanotube array layer.The beneficial effects of the practice of the present invention mainly has：1st, the pH electrodes of cored structure are covered, is conducive to the interference for overcoming extraneous water flow fluctuation to detect pH, improves sensitivity and the detection range of sensor.2nd, extend the service life of pH sensors with reference to double filter screen and the photocatalysis sterilization mode of different meshes, be applicable in multiple-quality water monitoring field.
Description
Technical field
The present invention relates to sensor field, more particularly to a kind of photoelectricity pH sensors and preparation method thereof.
Background technology
Water quality pH is the important indicator in monitoring water environment field.The important method that the monitoring to water quality pH uses at present
It is to use the pH sensors based on field-effect transistor, field-effect transistor is as signal adapter, and semiconductive thin film is as quick
Feel component.Its basic principle can be explained with aquation shelf theory：When semiconductive thin film is placed in aqueous solution, in aqueous solution
Hydrogen ion can form MOH, MO with film-、MOH2+Deng adsorbed state, so as to form electric double layer, surface potential is produced.H in solution+
Ion concentration is bigger, and surface potential is bigger, and the channel current change of field-effect transistor is bigger.Therefore, according to current signal and H+The correspondence of ion concentration, can detect pH in solution.In actual measurement, sensitive thin film is frequently with oxide semiconductor film
Material.This is because metal-oxide film is easy to aquation, the rate of rise of hydrated sheath is very fast so that the sensitivity of device, line
Property scope, response speed are all relatively good.
However, the major issue that the long-time stability of pH sensors, which are field-effect-transistor-based pH sensors, to be faced.
This is because Ag/AgCl reference electrodes are often used electrode.And the long-time stability of Ag/AgCl are poor, AgCl precipitations are easy
In coming off so that electrode potential fluctuates, can not normal use.On the other hand, the service life of field-effect-transistor-based pH sensors asks
Topic it is also contemplated that.In water body environment, various microorganisms, mushroom, algae in water body etc. can be attached to pH electrode long period of soaking
Electrode surface, influences the detection performance and service life of sensor.
The content of the invention
The technical problem to be solved in the present invention is sensor stability of the prior art is poor, service life is short.
In order to solve the above-mentioned technical problem, a kind of photoelectricity pH sensors based on field-effect transistor are disclosed in the present invention
And preparation method thereof, the technical scheme is that be implemented：
A kind of photoelectricity pH sensors, the photoelectricity pH sensors include：Shell, display module, one-chip computer module, at signal
Manage module, field-effect transistor, excitation source and pH electrodes；The shell includes first chamber and second chamber, and described first
Chamber is sealed chamber；The display module, one-chip computer module, signal processing module and field-effect transistor are arranged at the first chamber
It is indoor；The pH electrodes include platinum electrode and the sensitive electrode that is set in the platinum electrode, the platinum electrode and quick
The middle part of second chamber inner top is fixed in one end of sense electrode；The sensitive electrode is inner surface and outer surface load two
The titanium tube of titania nanotube array layer.
Preferably, the thickness of titanium dioxide nanotube array layer is 1~10 μm；Form the Nano tube array of titanium dioxide
The outside diameter of titania nanotube in layer is 100~150nm, draw ratio is 10~15.
Preferably, platinum electrode is located at the center of the sensitive electrode, is not contacted with the sensitive electrode；It is described
A diameter of 1~2mm of platinum electrode；The interior caliber of the sensitive electrode is 4~10mm, thickness is 2~5mm, be highly 3~
7cm；A height of 15~the 20cm of length and width of the shell.
Preferably, display module is connected with the one-chip computer module, the one-chip computer module and the signal processing module
It is connected, the signal processing module is connected with the source lead of the field-effect transistor, the grid of the field-effect transistor
Pin is connected with one end of the sensitive electrode, one end phase of the drain lead of the field-effect transistor and the platinum electrode
Even；When carrying out pH value detection, the field-effect transistor is in open mode, and the voltage between gate-to-source is arranged to Vgs
=1~3V, the voltage between Drain-Source are arranged to Vds=0.1~0.4V.
Preferably, the inside cavity side wall of second chamber is provided with least one excitation source, and the excitation source is ripple
Long scope is in the burst of ultraviolel light source of 250nm~420nm, 5~50min of irradiation time.
Preferably, the other end of sensitive electrode is connected with the first strainer, for filtering the small particle of 0.5~2um；It is described
The bottom of second chamber is connected with the second strainer, for preventing bulky grain thing of the particle diameter more than 0.1mm from entering the second inside cavity.
A kind of preparation method of photoelectricity pH sensors, the preparation method of the photoelectricity pH sensors include：
Step S1：Anodic oxidation reactions are carried out using two-probe method, titanium tube matrix are put into electrolyte, in the titanium tube
Respectively place a platinum filament on the inside of matrix and outside；Using the titanium tube matrix as anode, platinum filament is cathode, by the titanium tube matrix table
Face aoxidizes, and obtains the sensitive electrode of inner surface and outer surface carried titanium dioxide nanotube array layer；
Step S2：There is provided one has the shell of first chamber and second chamber, and the first chamber and second chamber connect,
Display module, one-chip computer module, signal processing module and field-effect transistor are arranged in the first chamber；It is wherein described
Display module is connected to the one-chip computer module, and the one-chip computer module is connected to the signal processing module, at the signal
Reason module is connected to the source lead of the field-effect transistor；
Step S3：The connected component of the first chamber and second chamber is sealed with fluid sealant, and forms the of sealing
One chamber；One end of platinum electrode and sensitive electrode is fixed on to the middle part of the inside top of second chamber, the sensitivity
Electrode sleeve forms pH electrodes in platinum electrode；The gate lead of the field-effect transistor is connected to the sensitive electrode
One end, the drain lead of the field-effect transistor are connected to one end of the platinum electrode；First strainer is socketed in described
Second worry net cover, is connected on the bottom of second chamber by the other end of sensitive electrode；At least one ultraviolet source is arranged at described
The internal side wall of two chambers.
Preferably, step S1 is further comprising the steps of：Before carrying out anodic oxidation reactions using two-probe method, by the titanium tube
Matrix is polished in chemical polishing solution, by the titanium tube matrix after polishing respectively in acetone, absolute ethyl alcohol and deionization
Respectively it is cleaned by ultrasonic 15~25min in water, drying is stand-by；When carrying out anodic oxidation reactions using bipolar electrode method, the electrolyte is
Glycerine electrolyte containing ammonium fluoride；The titanium tube matrix is aoxidized into 0.5~1.5h under 15~35V anodic oxidation voltages
Afterwards, the titanium dioxide nanotube array layer crystallized in titanium tube base inner surface and outer surface is made annealing treatment；Wherein anneal
Temperature is 350~550 DEG C, and heating rate is 1~3 DEG C/min, is kept the temperature as 2~4h.
Preferably, the thickness of titanium dioxide nanotube array layer is 1~10 μm；Form the Nano tube array of titanium dioxide
The outside diameter of titania nanotube in layer is 100~150nm, draw ratio is 10~15.
A kind of photoelectricity pH sensors, the application in water quality monitoring field.
The beneficial effects of the practice of the present invention mainly has：
1st, pH electrodes of the invention use specific Nano tube array of titanium dioxide Titanium pipe sleeve in platinum filament to electrode
Mode, overcomes the interference that extraneous water flow fluctuation detects pH.
2nd, the present invention utilizes the high surface area of the titanium tube of curved surface, the advantage of high load amount, improves photoelectricity pH sensors
Sensitivity and response speed.
3rd, the impurity such as the grains of sand, algae, microorganism, bacterium are filtered by designing the double filter screen of reasonable different meshes,
Microorganism, the bacterium of remaining are further killed in conjunction with photocatalysis sterilization mode, reach extension photoelectricity pH sensors uses the longevity
The purpose of life, is applicable in multiple-quality water monitoring field, the monitoring in especially complicated water quality field.
Brief description of the drawings
To more fully understand technical scheme, refer to it is following, for the prior art or embodiment progress
The attached drawing of explanation.These attached drawings will simply show section Example or prior art related products or method.
The essential information of these attached drawings is as follows：
Fig. 1 is photoelectricity pH sensor construction schematic diagrames in one embodiment.
In above-mentioned attached drawing, in reference numeral and its corresponding technical characteristic are listed in the table below by mainly sieve：
| Reference numeral | Corresponding technical characteristic |
| 1 | Shell |
| 2 | Excitation source |
| 3 | PH electrodes |
| 31 | Sensitive electrode |
| 32 | Platinum electrode |
| 4 | Field-effect transistor |
| 5 | Signal processing module |
| 6 | One-chip computer module |
| 7 | Display module |
It should be noted that these attached drawings are reference charts, sometimes for easy to protrude ins and outs, understand easy to reader,
Local pattern, shape may be shown using the gimmick of exaggeration, it is also possible to the width of lines, length, density,
Or the making choice property of size of attached drawing inscape highlight.For some embodiments, during implementation, it is related to
To the ratio of object, size, position, number etc. it is not absolutely required to implement in strict accordance with attached drawing.To realize the essence of the present invention
God, order, implementation personnel reasonably attached drawing can be combined and details on increase and decrease, and implementation also can from
The limitation of upper attached drawing.
Embodiment
Below in conjunction with attached drawing, further expansion is made to the technical solution in the embodiment of the present invention or beneficial effect and is retouched
State, it is clear that described embodiment be only the present invention some embodiments, and and it is not all.
" those skilled in the art " or its synonym referred in text, refers to a kind of such object：It can be known sheet
All ordinary technical knowledges of innovation and creation technical field before the applying date of patent application or priority date, can obtain
Know the prior art all in the field, and with the ability for applying normal experiment means before the date；If to be solved
Technical problem certainly can promote those skilled in the art to find technological means in other technologies field, it should also have from this
Related art, ordinary technical knowledge and the normal experiment before this application day or priority date are known in other technologies field
The ability of means.
The word with the indicating position such as " on ", " under ", "left", "right", " interior ", " outer " or position relationship is used in text,
Mainly due to the consideration understood easy to reader.These words are indicated based on relative bearing shown in the drawings or relative position pass
System, or the relative bearing usually put when in use of some objects or relative position relation, but might not indicate or secretly
Show absolute direction or position, therefore it is not intended that limiting the scope of the invention.
It is only used for distinguishing some key elements using " first ", " second ", " the 3rd " and similar word in text, without being understood that
To indicate or implying relative importance, any order, quantity are not indicated that yet.
Only for convenient description and understood using " level ", " vertical " and similar word in text, be not offered as requiring portion
Part is necessary for abswolute level or pendency in any embodiment, can have certain angle of inclination in a practical situation.
Unless refering in particular to, reply term " setting ", " installation ", " connected ", " connection " etc. make the understanding of broad sense.For example, connection
It can be understood as being fixedly connected, be detachably connected, or be integrally connected；It can be understood as mechanically connecting, or be electrically connected；It can manage
Solve and be indirectly connected to be connected directly, by intermediary, or the connection of two components interiors.For those skilled in the art
Speech, can understand the concrete meaning of above-mentioned term in the present invention as the case may be.
Unless refering in particular to, the other technologies term or scientific terminology that occur herein can have those skilled in the art from now
There is the ordinary meaning got in technology, if a term has a variety of ordinary meanings or explanation, reader should combine context
And the order of the present invention is rationally understood.
In addition, on the premise of not disclosed by the prior art, any technical characteristic or embodiment described in text, should regard
The intellectual achievement that performing creative labour produces has been made for applicant.
Embodiment one
As shown in Figure 1, the present invention provides a kind of photoelectricity pH sensors based on field-effect transistor 4.
As shown in Figure 1, the photoelectricity pH sensors include：At shell 1, display module 7, one-chip computer module 6, signal
Manage module 5, field-effect transistor 4, excitation source 2 and pH electrodes 3.Preferably, the shell 1 is the plastic shell of cuboid
1, a height of 15~20cm of length and width of shell 1.
The shell 1 includes first chamber and second chamber, first chamber and the second chamber sealed separation；It is described aobvious
Show that module 7, one-chip computer module 6, signal processing module 5 and field-effect transistor 4 are arranged in first chamber；The pH electrodes 3
Including platinum electrode 32 and the sensitive electrode 31 being set in the platinum electrode 32, the sensitive electrode 31 is for inner surface and outside
One end of the titanium tube of area load titanium dioxide nanotube array layer, the platinum electrode 32 and sensitive electrode 31 is fixed on second
The middle part of chamber inner top.The sensitive electrode 31 is inner surface and outer surface carried titanium dioxide nanotube array layer
Titanium tube.In the present embodiment, pH electrodes 3 using Nano tube array of titanium dioxide Titanium pipe sleeve loaded on platinum filament to electrode by the way of,
The sensitive diaphragm area for playing pH sensitizations exists only in the inner surface of metal titanium tube, titanium tube exterior surface area because not with platinum filament pair
Electrode is not directly facing therefore actual playing pH sensitizations.That is, actually detected is in titanium tube inner surface by confinement
Internal H+Ion.Therefore, the pH electrodes 3 of such special construction can overcome the interference that extraneous water flow fluctuation detects pH.Its
In, platinum electrode is platinum filament to electrode so that the stability of electrode is good, and chemical inertness is strong.Even if electrode is long-term in water body
Immersion, its physicochemical properties will not significant change.Ag/AgCl reference electrodes are substituted to electrode using platinum filament, overcome Ag/
The problem of AgCl reference electrode service lifes are short, and long-time stability are poor.
In the present embodiment, platinum electrode 32 is located at the center of the sensitive electrode 31, is not connect with sensitive electrode 31
Touch.Wherein, a diameter of 1~2mm of platinum electrode 32；The interior caliber of sensitive electrode 31 is 4~10mm, and thickness is 2~5mm, high
Spend for 3~7cm.Platinum electrode 32 is located at the center of sensitive electrode 31, is not contacted with sensitive electrode 31.On sensitive electrode
Titanium dioxide nanotube array layer thickness be 1~10 μm；Titanium dioxide in composition titanium dioxide nanotube array layer is received
The outside diameter of mitron is 100~150nm, and draw ratio is 10~15.In the present embodiment, sensitive electrode 31 is matrix by metal titanium tube,
By growing film of Nano tube array of titanium dioxide in the Anodic Oxidation of electrolyte containing F-.This is with key advantage：First, vertically
Nano-tube array structure helps to shorten H+Ion diffusion path, improves the response speed of pH detections.Secondly, compared to plane
The semiconductor sensitive electrode 31 of structure, the film of Nano tube array of titanium dioxide that the titanium tube of curved surface is loaded is more, surface area bigger,
Therefore effective work area of semiconductor sensitive membrane is increased, improves H+Ion is improved in the loading of sensitive electrode 31
The sensitivity of photoelectricity pH sensors and detection range.
In a preferred embodiment, the caliber of titanium tube matrix is 5mm, thickness 2mm, is highly 5cm；Platinum filament it is straight
Footpath is 1mm；The purity of titanium tube matrix is 99.4%.The thickness of titanium dioxide nanotube array layer is 6~7 μm；Form described two
The outside diameter of titania nanotube in titania nanotube array layer is 120~135nm, draw ratio is 10~13.
In the present embodiment, the display module 7 is connected with the one-chip computer module 6, the one-chip computer module 6 and the letter
Number processing module 5 is connected, and the signal processing module 5 is connected with the source lead of the field-effect transistor 4, the field-effect
The gate lead of transistor 4 is connected with one end of the sensitive electrode 31, the drain lead of the field-effect transistor 4 with it is described
One end of platinum electrode 32 is connected.When carrying out pH value detection, the field-effect transistor 4 is in open mode, gate-to-source
Between voltage be arranged to Vgs=1~3V, the voltage between Drain-Source is arranged to Vds=0.1~0.4V.
In the present embodiment, the signal processing module 5 includes current/voltage converter circuit, amplifying circuit, A/D conversion electricity
Road, output signal are sent to display module 7 after the processing of one-chip computer module 6 and show.Specifically, the current/voltage-converted electricity
Road uses OP37 operational amplifiers, and the current signal that working electrode produces is converted into voltage signal.The display screen is liquid crystal
Display screen.Voltage signal is amplified processing by the amplifying circuit INA122 amplifiers, and list is sent to after analog-to-digital conversion
Piece machine STM32.PH value is shown to liquid crystal display by STM32 chips as controller.
In a preferred embodiment, the field-effect transistor 4 be commercialization field-effect transistor, model
CD4007UB.Field-effect crystalline substance transistor is in open mode all the time, and the voltage between gate-to-source is arranged to Vgs=2V, leaks
Voltage between pole-source electrode is arranged to Vds=0.1V.Utilize the signal amplification of field-effect crystalline substance transistor, semiconductive thin film
The small potential change in surface can cause channel current Ids significantly to change, thus can in real time, quickly respond water
Body pH value changes.
In the present embodiment, the inside cavity side wall of the second chamber is provided with least one excitation source 2, in titanium dioxide
Excitation source 2 is set on the outside of titanium nano-tube array metal titanium tube, the photocatalytic activity of Nano tube array of titanium dioxide can be excited,
The problem of killing the materials such as the microorganism of surface attachment, overcoming photoelectricity pH sensor Long Service Lifes.Specifically, described swash
Light emitting source 2 is wave-length coverage in the burst of ultraviolel light source 2 of 250nm~420nm, 5~50min of irradiation time.
In a preferred embodiment, the burst of ultraviolel light source 2 is LED ultraviolet lamps, is symmetrically disposed on the second cavity
Internal two side.Specifically, the excitation source 2 is ultraviolet light of the wave-length coverage in 270nm~290nm, when preferably irradiating
Between 25~40min.
In the present embodiment, the other end of the sensitive electrode 31 is connected with the first strainer, can filter 0.5~2 μm small
Particulate matter.The bottom of the second chamber is connected with the second strainer, for preventing bulky grain thing of the particle diameter more than 0.1mm from entering the
Two inside cavities.
In a preferred embodiment, the other end of the sensitive electrode 31 is socketed with the first strainer, first filter
Net is HEPA (High efficiency particulate air Filter) strainer, and the small particle is bacterium and micro- life
One or more in thing.The other end of the platinum electrode 32 does not contact HEPA strainers.The bottom socket of the second chamber
There is the second worry net, second strainer is copper strainer, and the bulky grain is preferably the one or more in the grains of sand and algae.It is described
First strainer is different from the size of the second strainer, by design the double filter screen of reasonable different meshes filter the grains of sand, algae,
The impurity such as microorganism, bacterium, microorganism, the bacterium of remaining are further killed in conjunction with photocatalysis sterilization mode, reaches extension light
The purpose of the service life of electric pH sensors, is applicable in multiple-quality water monitoring field, the monitoring in especially complicated water quality field.
The photoelectricity pH sensors of the present embodiment, need not in detection of complex water quality for general pH sensors
Pretreatment, can directly detect.At present, many seawater detections use photometry, but photometry is complicated, and are unsuitable for measuring
Turbidity is higher, the more water body of suspended particulate.The present embodiment to 10mL seawater (being derived from Haikou City, Hainan Province white sand door park) into
Row pH is detected, the results showed that and there are different turbidity to show consistent pH value with the 10mL seawater samples of suspended particulate, and
Detection sensitivity is high.In addition, the photoelectricity pH sensors in the present embodiment still show good make after reusing 100 times
With performance, there is stability.
Embodiment two
The present invention provides a kind of preparation method of the photoelectricity pH sensors based on field-effect transistor, the photoelectricity pH sensings
The preparation method of device comprises the following steps：
Step S1：Anodic oxidation reactions are carried out using two-probe method, titanium tube matrix are put into electrolyte, in titanium tube matrix
A platinum filament is respectively placed in inner side and outside, is conducive to homoepitaxial of the titania nanotube in the inside and outside wall of pipe.In the present embodiment
Using titanium tube matrix as anode, platinum filament is cathode, and titanium tube base inner surface and outer surface are aoxidized, inner surface is obtained and outer surface is born
The sensitive electrode 31 of carrying of titanium dioxide nanotube array layer.In this implementation, the caliber of the titanium tube matrix is 5mm, and thickness is
2mm, is highly 5cm；A diameter of 1mm of the platinum filament；Spacing is 2mm between the anode and cathode.Preferably, the titanium tube
The purity of matrix is 99.4%.
Specifically, the step S1 is further comprising the steps of：
Before carrying out anodic oxidation reactions using two-probe method, titanium tube matrix is polished in chemical polishing solution, will be thrown
Titanium tube matrix after light is respectively cleaned by ultrasonic 15~25min in acetone, absolute ethyl alcohol and deionized water respectively, and drying is stand-by.
In one preferred embodiment, the polishing fluid includes volume ratio 1:4:5 HF, HNO3And H2O。
When carrying out anodic oxidation reactions using bipolar electrode method, the electrolyte is to contain ammonium fluoride (NH4F glycerine electricity)
Solve liquid.Wherein, it is 50 that the electrolyte, which includes volume ratio,:50~60:40 glycerine and deionized water, concentration for 0.2~
The ammonium fluoride of 0.27M.In a preferred embodiment, the electrolyte of reaction is the solution of 0.27M ammonium fluorides, solvent for water and
Glycerine volume ratio is 1:1 mixed solution.
After the titanium tube matrix finally is aoxidized 0.5~1.5h under 15~35V anodic oxidation voltages, make annealing treatment in titanium
The titanium dioxide nanotube array layer that pipe base inner surface and outer surface are crystallized；Wherein annealing temperature is 350~550
DEG C, heating rate is 1~3 DEG C/min, is kept the temperature as 2~4h.The thickness of the titanium dioxide nanotube array layer obtained in the present embodiment
Spend for 1~10 μm；Form the outside diameter of the titania nanotube in the titanium dioxide nanotube array layer for 100~150nm,
Draw ratio is 10~15.
In a preferred embodiment, after titanium tube matrix being aoxidized 1h under 25V anodic oxidation voltages, annealing makes
Titania nanotube crystallizes, and wherein annealing temperature is 450 DEG C, and heating rate is 2 DEG C/min, keeps the temperature 3h.
The effects of process parameters nanotube caliber size and nanotube length of anodic oxidation, the work provided in above-mentioned steps
Skill parameter area can ensure the generation of nano tube structure, but under different technological parameters (including electrolyte system, oxidation
Voltage, oxidization time, electrode spacing), the nanotube caliber size and nanotube length for preparing gained are different.
Step S2：There is provided one has the shell 1 of first chamber and second chamber, first chamber and the second chamber part
Connection, first chamber is arranged at by the display module 7, one-chip computer module 6, signal processing module 5 and field-effect transistor 4
It is interior；Wherein, the display module 7 is connected to the one-chip computer module 6, and the one-chip computer module 6 is connected to the signal processing
Module 5, the signal processing module 5 are connected to the source lead of the field-effect transistor 4.
Step S3：Connected component is sealed with fluid sealant, and forms the first chamber of sealing；By the platinum electrode 32 and
The middle part of the inside top of second chamber is fixed in one end of sensitive electrode 31, and the sensitive electrode 31 is sleeved on platinum filament electricity
PH electrodes 3 are formed on pole 32, the gate lead of the field-effect transistor 4 is connected to one end of the sensitive electrode 31, described
The drain lead of field-effect transistor 4 is connected to one end of the platinum electrode 32；First strainer is socketed in the sensitive electrical
Second worry net cover, is connected on the bottom of second chamber by the other end of pole 31；At least one burst of ultraviolel light source 2 is arranged at described
The internal side wall of two chambers.
In conclusion structure of the present invention using Nano tube array of titanium dioxide Titanium pipe sleeve loaded on platinum filament to electrode,
Be conducive to the interference for overcoming extraneous water flow fluctuation to detect pH, improve pH detection sensitivities and detection range.Using chemical inertness
Strong platinum electrode is used as the stability for electrode, being conducive to improve photoelectricity pH sensors.By designing reasonable different meshes
Double filter screen filters the impurity such as the grains of sand, algae, microorganism, bacterium, is further killed in conjunction with photocatalysis sterilization mode residual
Microorganism, the bacterium deposited, achieve the purpose that the service life for extending photoelectricity pH sensors, are applicable in multiple-quality water monitoring field, especially
It is the monitoring in complicated water quality field.So the present invention effectively overcomes various shortcoming of the prior art and has high industrial
Utility value.
Meeting in the range of the knowledge and ability level of those skilled in the art, the various embodiments that embodiment hereof refers to
Or technical characteristic is in the case where there is no conflict, can be mutually combined and be used as other alternative embodiment, these not by
Alternative embodiment come, that the limited quantity formed is combined by the technical characteristic of limited quantity is set out one by one, still falls within this hair
Also it is that those skilled in the art can be appreciated with reference to attached drawing and above or infer and draw in the technical scope of bright exposure.
Finally it is pointed out that embodiment cited hereinabove, is more typical, preferred embodiment of the invention, only
For describing in detail, explaining technical scheme, in order to which reader understands, the protection domain being not intended to limit the invention
Or application.Therefore, within the spirit and principles in the present invention any modification, equivalent replacement, improvement and so on and obtain
Technical solution, should all covered within protection scope of the present invention.
Claims (10)
1. a kind of photoelectricity pH sensors, it is characterised in that the photoelectricity pH sensors include：Shell, display module, microcontroller mould
Block, signal processing module, field-effect transistor, excitation source and pH electrodes；
The shell includes first chamber and second chamber, and the first chamber is sealed chamber；The display module, microcontroller
Module, signal processing module and field-effect transistor are arranged in first chamber；
The pH electrodes include platinum electrode and the sensitive electrode being set in the platinum electrode, the platinum electrode and sensitivity
The middle part of second chamber inner top is fixed in one end of electrode；The sensitive electrode loads dioxy for inner surface and outer surface
Change the titanium tube of titanium nanotube array layer.
2. photoelectricity pH sensors according to claim 1, it is characterised in that：
The thickness of the titanium dioxide nanotube array layer is 1~10 μm；Form in the titanium dioxide nanotube array layer
The outside diameter of titania nanotube is 100~150nm, draw ratio is 10~15.
3. photoelectricity pH sensors according to claim 1, it is characterised in that：
The platinum electrode is located at the center of the sensitive electrode, is not contacted with the sensitive electrode；The platinum filament electricity
A diameter of 1~2mm of pole；The interior caliber of the sensitive electrode is 4~10mm, thickness is 2~5mm, is highly 3~7cm；It is described
A height of 15~the 20cm of length and width of shell.
4. photoelectricity pH sensors according to claim 1, it is characterised in that：
The display module is connected with the one-chip computer module, and the one-chip computer module is connected with the signal processing module, institute
The source lead that signal processing module is stated with the field-effect transistor is connected, the gate lead of the field-effect transistor and institute
The one end for stating sensitive electrode is connected, and the drain lead of the field-effect transistor is connected with one end of the platinum electrode；
When carrying out pH value detection, the field-effect transistor is in open mode, and the voltage between gate-to-source is arranged to
Vgs=1~3V, the voltage between Drain-Source are arranged to Vds=0.1~0.4V.
5. photoelectricity pH sensors according to claim 1, it is characterised in that：
The inside cavity side wall of the second chamber is provided with least one excitation source, and the excitation source exists for wave-length coverage
The burst of ultraviolel light source of 250nm~420nm, 5~50min of irradiation time.
6. photoelectricity pH sensors according to claim 1, it is characterised in that：
The other end of the sensitive electrode is connected with the first strainer, for filtering the small particle of 0.5~2um；
The bottom of the second chamber is connected with the second strainer, for preventing bulky grain thing of the particle diameter more than 0.1mm from entering second
Inside cavity.
7. a kind of preparation method of photoelectricity pH sensors, it is characterised in that the preparation method of the photoelectricity pH sensors includes：
Step S1：Anodic oxidation reactions are carried out using two-probe method, titanium tube matrix are put into electrolyte, in the titanium tube matrix
A platinum filament is respectively placed in inner side and outside；Using the titanium tube matrix as anode, platinum filament is cathode, by the titanium tube matrix surface oxygen
Change, obtain the sensitive electrode of inner surface and outer surface carried titanium dioxide nanotube array layer；
Step S2：There is provided one has the shell of first chamber and second chamber, and first chamber and the second chamber connection will be aobvious
Show that module, one-chip computer module, signal processing module and field-effect transistor are arranged in the first chamber；Wherein described display
Module is connected to the one-chip computer module, and the one-chip computer module is connected to the signal processing module, the signal processing mould
Block is connected to the source lead of the field-effect transistor；
Step S3：The connected component of the first chamber and second chamber is sealed with fluid sealant, and forms the first chamber of sealing
Room；One end of platinum electrode and sensitive electrode is fixed on to the middle part of the inside top of second chamber, the sensitive electrode
It is sleeved on formation pH electrodes in the platinum electrode；The gate lead of the field-effect transistor is connected to the sensitive electrode
One end, the drain lead of the field-effect transistor are connected to one end of the platinum electrode；First strainer is socketed in described
Second worry net cover, is connected on the bottom of second chamber by the other end of sensitive electrode；At least one ultraviolet source is arranged at described
The internal side wall of two chambers.
8. the preparation method of photoelectricity pH sensors according to claim 7, it is characterised in that：The step S1 further include with
Lower step：
Before carrying out anodic oxidation reactions using two-probe method, the titanium tube matrix is polished in chemical polishing solution, will be thrown
The titanium tube matrix after light is respectively cleaned by ultrasonic 15~25min in acetone, absolute ethyl alcohol and deionized water respectively, and drying is treated
With；
When carrying out anodic oxidation reactions using bipolar electrode method, the electrolyte is the glycerine electrolyte containing ammonium fluoride；
After the titanium tube matrix is aoxidized 0.5~1.5h under 15~35V anodic oxidation voltages, make annealing treatment in titanium tube matrix
The titanium dioxide nanotube array layer that surface and outer surface are crystallized；Wherein annealing temperature is 350~550 DEG C, heating speed
Rate is 1~3 DEG C/min, is kept the temperature as 2~4h.
9. the preparation method of photoelectricity pH sensors according to claim 7, it is characterised in that：The titania nanotube
The thickness of array layer is 1~10 μm；The outside diameter for forming the titania nanotube in the titanium dioxide nanotube array layer is
100~150nm, draw ratio are 10~15.
10. one kind is according to claim 1~6 any one of them photoelectricity pH sensors, the application in water quality monitoring field.
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| CN114113223A (en) * | 2021-11-25 | 2022-03-01 | 徐州医科大学 | Preparation method of single-cell intracellular pH sensor based on nano-pipette |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102735733A (en) * | 2012-07-23 | 2012-10-17 | 重庆大学 | Electrode for determining concentration of nitrite in solution and manufacturing method of electrode |
| CN102998336A (en) * | 2011-09-16 | 2013-03-27 | Nxp股份有限公司 | pH sensor and manufacturing method |
| CN203849194U (en) * | 2014-05-24 | 2014-09-24 | 智胜化工股份有限公司 | Circulation type device for on-line detection of pH electrodes |
| CN106319600A (en) * | 2015-06-27 | 2017-01-11 | 重庆大学 | Preparation method for titanium dioxide nanotube array of inner surface of ultra-long fine titanium tube |
-
2017
- 2017-11-24 CN CN201711195359.9A patent/CN108007993B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102998336A (en) * | 2011-09-16 | 2013-03-27 | Nxp股份有限公司 | pH sensor and manufacturing method |
| CN102735733A (en) * | 2012-07-23 | 2012-10-17 | 重庆大学 | Electrode for determining concentration of nitrite in solution and manufacturing method of electrode |
| CN203849194U (en) * | 2014-05-24 | 2014-09-24 | 智胜化工股份有限公司 | Circulation type device for on-line detection of pH electrodes |
| CN106319600A (en) * | 2015-06-27 | 2017-01-11 | 重庆大学 | Preparation method for titanium dioxide nanotube array of inner surface of ultra-long fine titanium tube |
Non-Patent Citations (2)
| Title |
|---|
| RONGRONG ZHAO等: "A pH sensor based on the TiO2 nanotube array modified Ti electrode", 《ELECTROCHIMICA ACTA》 * |
| SAYED A. M. MARZOUK: "Improved Electrodeposited Iridium Oxide pH Sensor Fabricated on Etched Titanium Substrates", 《ANAL. CHEM.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114113223A (en) * | 2021-11-25 | 2022-03-01 | 徐州医科大学 | Preparation method of single-cell intracellular pH sensor based on nano-pipette |
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