CN108007993B - A kind of photoelectricity pH sensor and preparation method thereof - Google Patents
A kind of photoelectricity pH sensor and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to sensor technical field, a kind of photoelectricity pH sensor and preparation method thereof is disclosed, the photoelectricity pH sensor includes: the 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 set in first chamber；PH electrode includes platinum electrode and the sensitive electrode that is set in the platinum electrode, the intermediate position 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: 1, covering the pH electrode of cored structure, be conducive to the interference for overcoming extraneous water flow fluctuation to detect pH, improve the sensitivity and detection range of sensor.2, extend the service life of pH sensor in conjunction with the double filter screen of different meshes and photocatalysis sterilization mode, be applicable in multiple-quality water and monitor field.
Description
Technical field
The present invention relates to sensor field, in particular to a kind of photoelectricity pH sensor and preparation method thereof.
Background technique
Water quality pH is the important indicator in monitoring water environment field.The important method that the monitoring of water quality pH is used at present
It is using the pH sensor 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+Equal adsorbed states generate surface potential to form electric double layer.H in solution+
Ion concentration is bigger, and surface potential is bigger, and the channel current variation of field effect transistor is bigger.Therefore, according to current signal and H+The corresponding relationship of ion concentration can detecte out 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 range, response speed are all relatively good.
However, the long-time stability of pH sensor are the major issues that field-effect-transistor-based pH sensor faces.
This is because what is be often used to electrode is Ag/AgCl reference electrode.And the long-time stability of Ag/AgCl are poor, AgCl precipitating is easy
In falling off, so that electrode potential fluctuates, it can not normal use.On the other hand, the service life of field-effect-transistor-based pH sensor 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.
Summary of the invention
That the technical problem to be solved by the present invention is to sensor stabilities in the prior art is poor, service life is short.
In order to solve the above-mentioned technical problem, a kind of photoelectricity pH sensor based on field effect transistor is disclosed in the present invention
And preparation method thereof, the technical scheme is that be implemented:
A kind of photoelectricity pH sensor, the photoelectricity pH sensor include: shell, display module, one-chip computer module, at signal
Manage module, field effect transistor, excitation light source and pH electrode；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 set to the first chamber
It is indoor；The pH electrode includes platinum electrode and the sensitive electrode that is set in the platinum electrode, the platinum electrode and quick
The intermediate position 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；Display module is connected with the one-chip computer module, the one-chip computer module and the letter
Number processing module is connected, and the signal processing module is connected with the source lead of the field effect transistor, the field-effect crystalline substance
The gate lead of body pipe is connected with one end of the sensitive electrode, the drain lead of the field effect transistor and platinum filament electricity
One end of pole is connected.
Preferably, titanium dioxide nanotube array layer with a thickness of 1~10 μm；Form the Nano tube array of titanium dioxide
The outer 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, does not contact with the sensitive electrode；It is described
The diameter of platinum electrode is 1~2mm；The interior caliber of the sensitive electrode be 4~10mm, with a thickness of 2~5mm, be highly 3~
7cm；A height of 15~the 20cm of the length and width of the shell.
Preferably, when carrying out pH value detection, the field effect transistor is in the open state, between gate-to-source
Voltage is set as Vgs=1~3V, and the voltage between Drain-Source is set as Vds=0.1~0.4V.
Preferably, the inside cavity side wall of second chamber is provided at least one excitation light source, and the excitation light source is wave
Burst of ultraviolel light source of the long range in 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 large particle of the partial size greater than 0.1mm from entering the second inside cavity.
A kind of preparation method of photoelectricity pH sensor, the preparation method of the photoelectricity pH sensor include:
Step S1: anodic oxidation reactions are carried out using two-probe method, titanium tube matrix are put into electrolyte, in the titanium tube
On the inside of matrix and a platinum filament is respectively placed in outside；Using the titanium tube matrix as anode, platinum filament is cathode, by the titanium tube matrix table
Face oxidation, obtains the sensitive electrode of inner surface and outer surface carried titanium dioxide nanotube array layer；
Step S2: providing a shell with first chamber and second chamber, the first chamber and second chamber connection,
Display module, one-chip computer module, signal processing module and field effect transistor are set 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 sealant, and forms the of sealing
One chamber；One end of platinum electrode and sensitive electrode is fixed on to the intermediate position of the inside top of second chamber, the sensitivity
Electrode sleeve forms pH electrode 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 is socketed in the bottom of second chamber by the other end of sensitive electrode；At least one ultraviolet source is set to 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, dehydrated 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 voltage
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, titanium dioxide nanotube array layer with a thickness of 1~10 μm；Form the Nano tube array of titanium dioxide
The outer diameter of titania nanotube in layer is 100~150nm, draw ratio is 10~15.
A kind of application of photoelectricity pH sensor in water quality monitoring field.
The beneficial effects of the practice of the present invention mainly has:
1, pH electrode of the invention uses 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.
2, the present invention improves photoelectricity pH sensor using the high surface area of the titanium tube of curved surface, the advantage of high load amount
Sensitivity and response speed.
3, 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 that remaining is further killed in conjunction with photocatalysis sterilization mode, reach extension photoelectricity pH sensor uses the longevity
The purpose of life is applicable in multiple-quality water and monitors field, the especially monitoring in complicated water quality field.
Detailed description of the invention
Technical solution for a better understanding of the invention, can refer to it is following, for being carried out to the prior art or embodiment
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 structure schematic diagram in one embodiment.
In above-mentioned attached drawing, in appended drawing reference and its corresponding technical characteristic are listed in the table below by mainly sieve:
| Appended drawing reference | Corresponding technical characteristic |
| 1 | Shell |
| 2 | Excitation light source |
| 3 | PH electrode |
| 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, sometimes for convenient for prominent technical detail, to understand with reference to figure convenient for reader,
May pattern to part, shape be shown using the gimmick of exaggeration, it is also possible to the width of lines, length, density,
Or the size of attached drawing constituent element is selectively highlighted.For some embodiments, in the process of implementation, it is related to
To ratio, size, position, the number of object etc. it is not absolutely required to implement in strict accordance with attached drawing.Essence to realize the present invention
Mind, order, implementation personnel reasonably attached drawing can be combined and details on increase and decrease, and implementation method can not also by with
The limitation of upper attached drawing.
Specific embodiment
Below in conjunction with attached drawing, technical solution in the embodiment of the present invention or beneficial effect are made further expansion and are retouched
It states, it is clear that described embodiment is only some embodiments of the invention, and and not all.
" those skilled in the art " or its synonym referred in text is to refer to a kind of such object: its knowable
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 there is the ability using routine experiment means before the date；If solved
Certainly the technical issues of, can promote those skilled in the art to find technological means in other technologies field, should also have from this
Related art, ordinary technical knowledge and the routine experiment before this application day or priority date are known in other technologies field
The ability of means.
The word with the indicating positions such as "upper", "lower", "left", "right", "inner", "outside" or positional relationship is used in text,
Mainly due to the considerations of understanding convenient for reader.These words indicate that relative bearing based on the figure or relative position are closed
System or some objects relative bearing or relative positional relationship usually put when in use, but might not indicate or secretly
Show absolute direction or position, therefore should not be understood as limiting the scope of the invention.
It is only used for distinguishing some elements using " first ", " second ", " third " and similar word in text, and cannot understand
For indication or suggestion relative importance, any sequence, quantity are not indicated yet.
It is not offered as requiring portion only for facilitating description and understanding using "horizontal", "vertical" and similar word in text
Part is necessary for abswolute level or pendency in any embodiment, is can be in a practical situation with certain tilt angle.
Unless refering in particular to, the understanding of broad sense is made in reply term " setting ", " installation ", " connected ", " connection " etc..For example, connection
It can be understood as being fixedly connected, be detachably connected, or be integrally connected；It can be understood as being mechanically connected, or electrical connection；It can manage
Solution to be connected directly, indirectly connected through an intermediary or the connection of two components interiors.For those skilled in the art
Speech, the specific meanings of the above terms in the present invention can be understood according to specific conditions.
Unless refering in particular to, the other technologies term or scientific term occurred 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 order of the invention is rationally understood.
In addition, under the premise of not disclosed by the prior art, any technical characteristic or embodiment recorded in text should be regarded
For the intellectual achievement that applicant has made creative labor and generates.
Embodiment one
As shown in Figure 1, the present invention provides a kind of photoelectricity pH sensor based on field effect transistor 4.
As shown in Figure 1, the photoelectricity pH sensor includes: including at shell 1, display module 7, one-chip computer module 6, signal
Manage module 5, field effect transistor 4, excitation light source 2 and pH electrode 3.Preferably, the shell 1 is the plastic shell of cuboid
1, a height of 15~20cm of the length and width of shell 1.
The shell 1 includes first chamber and second chamber, the first chamber and 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 set in first chamber；The pH electrode 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 intermediate position 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 electrode 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 sensitization exists only in the inner surface of metal titanium tube, titanium tube exterior surface area because not with platinum filament pair
Electrode is directly facing therefore the practical pH sensitization that do not play.That is, actually detected is by confinement in titanium tube inner surface
Intracorporal H+Ion.Therefore, the interference that the pH electrode 3 of such special construction can overcome extraneous water flow fluctuation to detect pH.Its
In, platinum electrode is platinum filament to electrode, so that the stability of electrode is good, chemical inertness is strong.Even if electrode is long-term in water body
It impregnates, physicochemical properties will not significant change.Ag/AgCl reference electrode is substituted to electrode using platinum filament, overcomes Ag/
AgCl reference electrode service life is short, the poor problem of long-time stability.
In the present embodiment, platinum electrode 32 is located at the center of the sensitive electrode 31, does not connect with sensitive electrode 31
Touching.Wherein, the diameter of platinum electrode 32 is 1~2mm；The interior caliber of sensitive electrode 31 is 4~10mm, high with a thickness of 2~5mm
Degree is 3~7cm.Platinum electrode 32 is located at the center of sensitive electrode 31, does not contact with sensitive electrode 31.On sensitive electrode
Titanium dioxide nanotube array layer with a thickness of 1~10 μm；Titanium dioxide in composition titanium dioxide nanotube array layer is received
The outer 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: firstly, vertical
Nano-tube array structure helps to shorten H+Ion diffusion path improves the response speed of pH detection.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, and surface area is 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 and detection range of photoelectricity pH sensor.
In a preferred embodiment, the caliber of titanium tube matrix is highly 5cm with a thickness of 2mm for 5mm；Platinum filament it is straight
Diameter is 1mm；The purity of titanium tube matrix is 99.4%.Titanium dioxide nanotube array layer with a thickness of 6~7 μm；Form described two
The outer 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 the open state, gate-to-source
Between voltage be set as Vgs=1~3V, the voltage between Drain-Source is set as 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 amplifier, and the current signal that working electrode generates is converted into voltage signal.The display screen is liquid crystal
Display screen.Voltage signal is amplified processing by the amplifying circuit INA122 amplifier, and list is sent to after analog-to-digital conversion
Piece machine STM32.STM32 chip is shown to liquid crystal display as controller, by pH value.
In a preferred embodiment, the field effect transistor 4 is the field effect transistor of commercialization, model
CD4007UB.Field-effect crystalline substance transistor is in the open state always, and the voltage between gate-to-source is set as Vgs=2V, leakage
Voltage between pole-source electrode is set as 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
The variation of body pH value.
In the present embodiment, the inside cavity side wall of the second chamber is provided at least one excitation light source 2, in titanium dioxide
Excitation light 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 substances such as the microorganism of surface attachment, overcoming photoelectricity pH sensor Long Service Life.Specifically, described swash
Light emitting source 2 is burst of ultraviolel light source 2 of the wave-length coverage in 250nm~420nm, 5~50min of irradiation time.
In a preferred embodiment, the burst of ultraviolel light source 2 is LED ultraviolet lamp, is symmetrically disposed on the second cavity
Internal two sidewalls.Specifically, the excitation light 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 large particle of the partial size greater 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 of object is a variety of.The other end of the platinum electrode 32 does not contact HEPA strainer.The bottom of the second chamber is socketed
There is the second worry net, second strainer is copper strainer, and the bulky grain is preferably one of the grains of sand and algae or a variety of.It is described
First strainer is different from the size of the second strainer, filtered by designing the double filter screen of reasonable different meshes the grains of sand, algae,
The impurity such as microorganism, bacterium further kill microorganism, the bacterium of remaining in conjunction with photocatalysis sterilization mode, reach extension light
The purpose of the service life of electric pH sensor is applicable in multiple-quality water and monitors field, the especially monitoring in complicated water quality field.
The photoelectricity pH sensor of the present embodiment does not need for general pH sensor in detection of complex water quality
Pretreatment, can directly detect.Currently, many seawater detections use photometry, but photometry is complicated for operation, and is 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 detection, the results showed that the 10mL seawater sample with different turbidity and suspended particulate shows consistent pH value, and
Detection sensitivity is high.In addition, the photoelectricity pH sensor in the present embodiment is still shown good make after reusing 100 times
With performance, there is stability.
Embodiment two
The present invention provides a kind of preparation method of photoelectricity pH sensor based on field effect transistor, the photoelectricity pH sensing
The preparation method of device the following steps are included:
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 inside and outside, is conducive to titania nanotube in the homoepitaxial of 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, and obtains inner surface and outer surface is negative
The sensitive electrode 31 of carrying of titanium dioxide nanotube array layer.In this implementation, the caliber of the titanium tube matrix is 5mm, with a thickness of
2mm is highly 5cm；The diameter of the platinum filament is 1mm；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, dehydrated alcohol and deionized water respectively, and drying is stand-by.?
In one preferred embodiment, the polishing fluid includes HF, HNO of volume ratio 1:4:53And H2O。
When carrying out anodic oxidation reactions using bipolar electrode method, the electrolyte is to contain ammonium fluoride (NH4F glycerine electricity)
Solve liquid.Wherein, the electrolyte include volume ratio be 50:50~60:40 glycerine and deionized water, concentration be 0.2~
The ammonium fluoride of 0.27M.In a preferred embodiment, the electrolyte of reaction be 0.27M ammonium fluoride solution, solvent be water and
Glycerine volume ratio is the mixed solution of 1:1.
After the titanium tube matrix is finally aoxidized 0.5~1.5h under 15~35V anodic oxidation voltage, 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 titanium dioxide nanotube array layer obtained in the present embodiment
Degree is 1~10 μm；Form the titania nanotube in the titanium dioxide nanotube array layer outer diameter be 100~150nm,
Draw ratio is 10~15.
In a preferred embodiment, after titanium tube matrix being aoxidized 1h under 25V anodic oxidation voltage, annealing makes
Titania nanotube crystallization, 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, work provided in above-mentioned steps
Skill parameter area can guarantee the generation of nano tube structure, but under different technological parameters (including electrolyte system, oxidation
Voltage, oxidization time, electrode spacing), it prepares resulting nanotube caliber size and nanotube length is different.
Step S2: a shell 1 with first chamber and second chamber, the first chamber and second chamber part are provided
Connection, is set to first chamber for 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 sealant, and forms the first chamber of sealing；By the platinum electrode 32 and
The intermediate position 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 electrode 3 is 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 is socketed in the bottom of second chamber by the other end of pole 31；At least one burst of ultraviolel light source 2 is set to described
The internal side wall of two chambers.
In conclusion the present invention uses structure of the 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 sensitivity and detection range.Using chemical inertness
Strong platinum electrode is used as the stability for being conducive to improve photoelectricity pH sensor to electrode.By designing reasonable different meshes
Double filter screen filters the impurity such as the grains of sand, algae, microorganism, bacterium, further kills in conjunction with photocatalysis sterilization mode residual
Microorganism, the bacterium deposited achieve the purpose that the service life for extending photoelectricity pH sensor, are applicable in multiple-quality water and monitor field, especially
It is the monitoring in complicated water quality field.So the present invention effectively overcomes various shortcoming in the prior art and has high industrial
Utility value.
Within the scope of the knowledge and ability level for meeting those skilled in the art, various embodiments that embodiment hereof refers to
Or technical characteristic is in the absence of conflict, can be combined with each other and as other alternative embodiment, these not by
Alternative embodiment coming, combining the limited quantity formed by the technical characteristic of limited quantity is set out one by one, still falls within this hair
It is also that those skilled in the art can be appreciated in conjunction with attached drawing and above or infer and obtain in the technical scope of bright exposure.
Finally it should be pointed out that embodiment cited hereinabove, is more typical, preferred embodiment of the invention, only
For being described in detail, explaining technical solution of the present invention, in order to reader's understanding, the protection scope 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 be all included within protection scope of the present invention.
Claims (10)
1. a kind of photoelectricity pH sensor, which is characterized in that the photoelectricity pH sensor includes: shell, display module, single-chip microcontroller mould
Block, signal processing module, field effect transistor, excitation light source and pH electrode；
The shell includes first chamber and second chamber, and the first chamber is sealed chamber；The display module, single-chip microcontroller
Module, signal processing module and field effect transistor are set in first chamber；
The pH electrode includes platinum electrode and the sensitive electrode that is set in the platinum electrode, the platinum electrode and sensitivity
The intermediate position of second chamber inner top is fixed in one end of electrode；The sensitive electrode is that inner surface and outer surface load dioxy
Change the titanium tube of titanium nanotube array layer；
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
It states signal processing module to be connected with the source lead of the field effect transistor, 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.
2. photoelectricity pH sensor according to claim 1, it is characterised in that:
The titanium dioxide nanotube array layer with a thickness of 1~10 μm；It forms in the titanium dioxide nanotube array layer
The outer diameter of titania nanotube is 100~150nm, draw ratio is 10~15.
3. photoelectricity pH sensor according to claim 1, it is characterised in that:
The platinum electrode is located at the center of the sensitive electrode, does not contact with the sensitive electrode；The platinum filament electricity
The diameter of pole is 1~2mm；The interior caliber of the sensitive electrode is 4~10mm, with a thickness of 2~5mm, be highly 3~7cm；It is described
A height of 15~the 20cm of the length and width of shell.
4. photoelectricity pH sensor according to claim 1, it is characterised in that:
When carrying out pH value detection, the field effect transistor is in the open state, and the voltage between gate-to-source is set as
Vgs=1~3V, the voltage between Drain-Source are set as Vds=0.1~0.4V.
5. photoelectricity pH sensor according to claim 1, it is characterised in that:
The inside cavity side wall of the second chamber is provided at least one excitation light source, and the excitation light source is that wave-length coverage exists
The burst of ultraviolel light source of 250nm~420nm, 5~50min of irradiation time.
6. photoelectricity pH sensor 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 large particle of the partial size greater than 0.1mm from entering second
Inside cavity.
7. a kind of preparation method of photoelectricity pH sensor, which is characterized in that the preparation method of the photoelectricity pH sensor 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 inside and outside；Using the titanium tube matrix as anode, platinum filament is cathode, by the titanium tube matrix surface oxygen
Change, obtains the sensitive electrode of inner surface and outer surface carried titanium dioxide nanotube array layer；
Step S2: a shell with first chamber and second chamber, the first chamber and second chamber connection are provided, will be shown
Show that module, one-chip computer module, signal processing module and field effect transistor are set in the first chamber；The wherein 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 sealant, and forms the first chamber of sealing
Room；One end of platinum electrode and sensitive electrode is fixed on to the intermediate position of the inside top of second chamber, the sensitive electrode
It is sleeved on formation pH electrode 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 is socketed in the bottom of second chamber by the other end of sensitive electrode；At least one ultraviolet source is set to described
The internal side wall of two chambers.
8. the preparation method of photoelectricity pH sensor 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, dehydrated alcohol and deionized water respectively, drying to
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 voltage, 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 sensor according to claim 7, it is characterised in that: the titania nanotube
Array layer with a thickness of 1~10 μm；The outer diameter for forming the titania nanotube in the titanium dioxide nanotube array layer is
100~150nm, draw ratio are 10~15.
10. a kind of application of photoelectricity pH sensors described in any item according to claim 1~6 in water quality monitoring field.
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| CN102998336A (en) * | 2011-09-16 | 2013-03-27 | Nxp股份有限公司 | pH sensor and manufacturing method |
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| 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 |
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