CN105044190A - Nano-porous sensor and production method thereof - Google Patents
Nano-porous sensor and production method thereof Download PDFInfo
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- CN105044190A CN105044190A CN201510390979.2A CN201510390979A CN105044190A CN 105044190 A CN105044190 A CN 105044190A CN 201510390979 A CN201510390979 A CN 201510390979A CN 105044190 A CN105044190 A CN 105044190A
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Abstract
The invention belongs to the field of trace oxygen content monitoring, and concretely relates to a nano-porous sensor and a production method thereof. The sensor comprises a sensor main body, an oxygen permeation membrane, a push rod and a pedestal arranged in a reaction chamber in the sensor main body, and a working electrode and a counter electrode arranged on the push rod, the working electrode and the counter electrode are respectively connected with an electrode connector through a leading wire, the reaction chamber is filled with a reaction electrolyte, the reaction surface of the working surface is a porous structure, and the pore diameter is 60-100nm. The nano-porous sensor can realize precious measurement of the PPB-level oxygen content under conditions with extremely low oxygen content and extremely high reaction speed requirements.
Description
Technical field
The invention belongs to micro-oxygen content monitoring field, be specifically related to a kind of nanoporous sensor and preparation method thereof.
Background technology
Current China electricity power supply 80% is by thermal power generation, and 6% is by nuclear power generation.Oxygen level in heat power plant boiler feedwater and the moisturizing of nuke nuclear island is an important indicator needing monitoring, because in the environment of High Temperature High Pressure, oxygen has great activity, be very easily the furnace wall of iron with boiler and dynamic material, blade generation chemical reaction, generate Fe3O4, trivalent Fe3+ ferric ion is cathodic depolarization agent, corrosion can be formed to metal itself, furnace wall forms Ferric oxide scale and not only hinders heat transfer, even more serious harm produces underdeposit corrosion. metallic walls will soon be made thinning, cause unbalance stress, situation seriously can cause boiler wall corrosion failure, the water vapor of unexpected generation can cause boiler or nuclear island blast, form the pernicious person and equipment breakdown, economic loss is serious, social influence is extremely bad.
In addition, in beer, beverage, biopreparate manufacture process with encapsulation before, oxygen level is also an important monitoring index.Because oxygen level is higher in beer, beverage, biopreparate, quality is lower, is more not easy to preserve; Oxygen level is lower, and quality is higher, and the shelf-life is longer.To the monitoring of the oxygen level in the production run of the said goods, there is very real economic worth.
Trace P PB level dissolved oxygen sensing detection technology is mainly used in above-mentioned fuel-burning power plant, nuclear power station, brewery and the relevant industries such as medicine, bioengineering, particularly for the content requirement extremely extremely low and operating mode that reaction velocity is high of stringent, oxygen level of oxygen in water, to ensure the normal operation of these industry related procedure, guarantee the safety in production of industry, improve the product quality of industry.
Due to the measuring accuracy of PPB level will be reached, require Quick Measurement again, have great difficulty in multinomial technical fields such as sensor, electrode, structure and selections, therefore completely domestic in like product on domestic market PPB level sensing detection equipment is in space state always.
Summary of the invention
For the problem that current home equipment is existing in PPB level dissolved oxygen sensing detection technology, the object of this invention is to provide a kind of nanoporous sensor and preparation method thereof for PPB level dissolved oxygen sensing detection.
Utilize a kind of electrochemical alloy of novelty-go alloyage to prepare the golden working electrode with the reaction surface of three-dimensional manometer pore structure, the reaction surface of the nano-porous structure obtained compared to existing technology in the reaction surface of smooth surface on reaction area, have great raising.
For reaching above object, the technical solution used in the present invention is a kind of nanoporous sensor, comprise sensor main body, oxygen permeation membrane, be arranged in described sensor main body reaction chamber in push rod and base, be arranged on working electrode on described push rod and to electrode, described working electrode and to electrode all by lead-in wire connecting electrode joint, reaction electrolytic solution is filled in described reaction chamber, the reaction surface of wherein said working electrode is porous structure, and the diameter in hole is 60-100nm.
Further, the golden cylindrical shell of described working electrode to be one end be shape for hat reaction surface.
Further, described is solenoid type filamentary silver to electrode.
Further, described oxygen permeation membrane is fastened on described sensor main body front end by body cover.
For reaching above object, the invention also discloses a kind of preparation method for above-described nanoporous sensor, comprising the following steps:
A () prepares sensor main body, push rod, base, body cover and oxygen permeation membrane;
B () makes working electrode, working electrode reaction surface is carried out polishing and clean, and adopt electrochemical alloy-go alloyage to process described reaction surface, the reaction surface after process presents porous structure, and the diameter in hole is 60-100nm; Working electrode after process is placed in push rod top, the hollow-core construction of the lead-in wire in working electrode by push rod and base is drawn;
C () makes electrode, will carry out tempering and grinding process to electrode, outside around push rod to electrode retaining collar by after process, is drawn to the lead-in wire of electrode by the hollow-core construction of push rod and base;
D () will be assembled with working electrode, be fixed in the reaction chamber of sensor main body inside, by working electrode and the electrode contact to the lead-in wire connecting sensor of electrode to the push rod of electrode and base;
(e) ready reaction electrolytic solution, and be filled in the reaction chamber in sensor main body, by body cover, oxygen permeation membrane is arranged on sensor front end.
Further, in step (a), described sensor main body, body cover, base adopt polyoxymethylene to make, and described oxygen permeation membrane, push rod adopt teflon to make.
Further, in step (b), prepare a golden cylinder, be processed into the Cylinder Shell that one end is shape for hat reaction surface, polishing cleaning is carried out to described shape for hat reaction surface, and adopts electrochemical alloy-go alloyage to process described reaction surface, golden Cylinder Shell is embedded push rod top, and lead-in wire is drawn by the hollow-core construction of push rod and base in golden Cylinder Shell, working electrode completes.
Further, in step (c), prepare a filamentary silver, carry out tempering and grinding process to described filamentary silver, filamentary silver is looped around push rod periphery, described filamentary silver one end arranges lead-in wire, and draw lead-in wire by the hollow-core construction of push rod and base, electrode fabrication is completed.
Further, in step (e), described reaction electrolytic solution is potassium chloride and potassium hydroxide mixed liquor.
Effect of the present invention is:
1. through the reaction surface surface of pretreated working electrode, define three-dimensional manometer pore structure, nano aperture is greatly about 60-100nm, nano-pore thickness is about 5 μm, the active area of this working electrode reaction surface is than about 5 times of active area ratio being the smooth reaction surface working electrode of identical material, and reaction area reaches 108.66mm
2, chemical property is the working electrode of smooth surface higher than reaction surface far away.The content measuring trace dissolved oxygen in water is low, and reaction velocity is fast, shows fabulous stability.
2. relative to working electrode, to the surface area of electrode larger (comparing for 70:1 the reaction area of electrode and working electrode), increase the electrochemical activity of electrode, prevent current spread on the impact of measurement data, and can ensure that polarizing voltage adds on the working electrode (s completely, ensure that working electrode and can accurately control the polarizing voltage between electrode.Achieve response fast (reaction velocity is within 30 seconds), highly sensitive, and have low-down zero current (aftercurrent, system residual electric current of the present invention is below 0.8nA).
3. special electrode structure and special material can eliminate oxygen electrode (working electrode and to the electrode) counter diffusion of interior oxygen and the leakage current of electrode.
4. the supporting measuring instrument detection speed of sensor is fast, and stability is high, and micro content oxygen accuracy of detection is high.
Nanoporous sensor connection instrument provided by the invention can supply water to fuel-burning power plant burning boiler, nuclear island of nuclear power station circular water replenishing, medicine and bioengineering reagent etc. are the on-line monitoring of PPB level to dissolved oxygen content in solution, be suitable for that oxygen level is extremely low and reaction velocity requires high various operating modes, at 10mM (NH4) 2Fe (SO4) 2 and 1mMCu
2+square-wave test result in solution further illustrates the electrochemical activity of housing cap gold electrode can far away higher than the electrochemical activity of smooth gold electrode.
Accompanying drawing explanation
Fig. 1 is the cut-open view of the sensor of nanoporous described in the embodiment of the present invention;
Fig. 2 is the partial enlarged drawing of the working electrode of the sensor of nanoporous described in the embodiment of the present invention;
Fig. 3 is the process schematic that electrochemical alloy described in the specific embodiment of the invention-go alloyage forms the nano-porous structure of working electrode surface;
Fig. 4 is the enlarged drawing of the porous structure of the working electrode surface relying on described electrochemical alloy-go alloyage to be formed in the specific embodiment of the invention;
Fig. 5 is the sectional drawing of the porous structure of the working electrode surface relying on described electrochemical alloy-go alloyage to be formed in the specific embodiment of the invention;
In figure: 1-temperature electrode, 2-oxygen permeation membrane, 3-body cover, 4-working electrode, 5-push rod, 6-is to electrode, and 7-sensor main body, 8-the one O type circle, 9-the 2nd O type circle, 11-goes between, 12-base, 13-electrode contact, 14-reaction chamber.
Embodiment
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
As shown in Figure 1, nanoporous sensor provided by the invention have employed two electrode oligodynamical oxygen sensors structure (polarographic oxygen electrode), comprise sensor main body, body cover, reaction chamber, push rod, base, working electrode, to electrode, oxygen permeation membrane, reaction electrolytic solution (pharmacy response), lead-in wire (insulator pin) etc.
Nanoporous sensor provided by the invention, adopts the sensor main body 7, base 12, the body cover 3 that are made by polyoxymethylene, and forming a volume in sensor main body 7 is 9.0cm
3the reaction chamber 14 of left and right, can place push rod 5 and base 12 in reaction chamber 14, and wherein one end of push rod 5 is connected (push rod 5 and base 12 are all hollow structure) with base 12.Push rod 5 is made by teflon, is the column type of hollow; Use the plastic foil (as PTFE, PFA material) of 30nm thickness to be processed as oxygen permeation membrane, and this oxygen permeation membrane is assemblied in main body leading portion, and can body cover (3) precession be passed through and be fastened on the front end (test side) of sensor.
As shown in Figure 2, working electrode adopts the gold quality cylindrical material of 99.99% to make, and gold right cylinder is processed into the cylindrical shell that one end is shape for hat reaction surface, enclosure interior hollow, inside is also provided with temperature electrode 1, and draws the electrode wires of temperature electrode 1 from inside.The thickness of shape for hat reaction surface is 1mm, and surface curvature radius is 100mm, and maximum open part diameter of a circle is Φ=5mm (surface flux diameter), and the surface area of shape for hat reaction surface is 19.86mm
2, electrochemical alloy-go alloyage to process, to obtain nano-porous structure is adopted to shape for hat reaction surface.Non-shape for hat reaction surface one end of working electrode is embedded the top of the push rod 5 of hollow, and (insulation) of drawing in working electrode lead-in wire 11 to be drawn with the hollow structure of base 12 by push rod 5 and is connected to the electrode contact 13 (also again electrode contact 13 will be connected the polarizing voltage end of outside in subsequent step) of sensor, the making of electrode of finishing the work.
The filamentary silver of 100% content is adopted to make to electrode, filamentary silver diameter 1mm, after pre-service (tempering and polishing), form coarse reaction surface, then the filamentary silver after process is made diameter 1cm solenoid type, and it is peripheral to be looped around columniform push rod 5, one end of filamentary silver arranges (insulation) lead-in wire 11, and drawn the electrode contact 13 (also again electrode contact 13 will be connected outside polarizing voltage end in subsequent step) of insulator pin connecting sensor by push rod 5 and the hollow-core construction of base 12, the making of complete paired electrode.
In the reaction chamber of nanoporous sensor provided by the present invention, need to fill reaction electrolytic solution (pharmacy response), reaction electrolytic solution is potassium chloride (KCL) and potassium hydroxide (KOH) mixed liquor, and the blending ratio of potassium chloride (KCL) and potassium hydroxide (KOH) is 900:1.
Working electrode 4 will be assembled with, to be threaded connection in the reaction chamber 14 being fixed on sensor main body 7 inside (in the present embodiment to the push rod 5 of electrode 6 and base 12, by the bottom of sensor main body 7, also arrange in pairs or groups O type circle 8 and the 2nd O type circle 9 sealed in the position be threaded), the electrode contact 13 of the sensor be connected with to the lead-in wire 11 of electrode 6 by working electrode 4 connects outside polarizing voltage end again, subsequently, in reaction chamber 14, reaction electrolytic solution is filled from the front end of sensor main body 7, and the body cover 3 being assembled with oxygen permeation membrane 2 is fastened on the front end of sensor main body 7 by screw thread precession, make working electrode 4 and electrode 6 be immersed in the reaction electrolytic solution in reaction chamber 14.So far, nanoporous sensor production provided by the present invention is complete.The polarization operating voltage of sensor is 0.68-8.0V.
The shape for hat reaction surface of the working electrode of nanoporous sensor provided by the present invention is nano-porous structure, and the preparation of this structure adopts a kind of simple and effective electrochemical alloy-go alloyage to realize, namely at ZnCl
2in/BA (phenmethylol) electrolytic solution, the shape for hat reaction surface of smooth (not the processing) of working electrode is carried out to the scan round (as shown in Figure 3) of certain number of times, Au-Zn alloy is formed on the surface of shape for hat reaction surface by electro-deposition Zn, then component Zn comparatively active in alloy is removed, through the shape for hat reaction surface of working electrode prepared by above method, there is the high-specific surface area of nano-pore structure, increase the surface area of working electrode reaction surface and the roughness of reaction surface.By controlling preparation temperature and scan round number of times, obtain the working electrode of the shape for hat reaction surface with three-dimensional manometer pore structure.
Polishing cleaning is carried out to the shape for hat reaction surface of the working electrode of nanoporous sensor provided by the present invention, and adopts electrochemical alloy-go the step of alloyage process as follows:
(1) the shape for hat reaction surface of the working electrode (golden) of nanoporous sensor first uses 200 orders, 500 orders, 100 object sand paper polish successively, and all use ultrasound wave to clean 5 minutes to shape for hat reaction surface after each polishing, and with the alumina powder polishing of 0.05 μm; Use 100% acetone soln, 100% ethanolic solution, distilled water to carry out ultrasonic cleaning to shape for hat reaction surface after bruting process terminates successively, each scavenging period is 5 minutes, and final drying is stand-by;
(2) the anhydrous ZnCl of 10.8g is got
2to be dissolved in 50m1 phenmethylol (BA) as electrolytic solution, to be heated to 60 DEG C and to make ZnCl
2dissolve, now ZnCl
2concentration be 1.6Mol;
(3) three-electrode electro Chemical workstation is adopted, zinc metal sheet is as auxiliary electrode and contrast electrode, the working electrode (golden) of nanoporous sensor is working electrode, three electrodes are all placed in same electrolytic cell, wherein, the shape for hat reaction surface of working electrode (golden) is exposed to the geometric area in electrolytic solution is 19.86mm
2.The speed that electrochemical workstation carries out scan round is 10mvS
-1, successively from open circuit potential → 0.72V → 1.88V, and then from 1.88V → 0.72V, iterative cycles.After the cycle index of about 40 times, take out working electrode (golden), use 100% phenmethylol, 100% ethanol, distilled water to clean successively.
Whole preprocessing process directly carries out in atmosphere.
To nanoporous sensor provided by the present invention to carry out the step of tempering and grinding process to electrode as follows:
(1) diameter of 100% content is adopted to be the filamentary silver of 1mm, temperature 48 hours temper in 180 degrees Celsius;
(2) then do grinding process with 500 order sand paper to filamentary silver surface, form coarse reaction surface, 100% ethanol, distilled water clean;
(3) filamentary silver is made solenoid type, solenoid diameter 1cm, cut to lengthen makes solenoidal reaction area be that about 70 times of the surface area of the shape for hat reaction surface of working electrode (namely reach 2000mm to the reaction area of electrode
2).
Principle of work of the present invention:
The electrode adopting nanoporous sensor provided by the invention to adopt belongs to micro-polarographic oxygen electrode, form by working electrode (golden negative electrode) with to electrode (silver anode), working electrode and to electrode be immersed in reaction electrolytic solution in, by oxygen permeation membrane (as PTFE, PFA) and reaction Thin Electrolyte Layer, electrode and water sample to be measured are separated.The polarization operating voltage that in actual measurement process, nanoporous sensor applies is 0.68V, sensor is placed in water sample to be measured, oxygen in water sample to be measured, by arriving the surface of the shape for hat reaction surface of golden working electrode after ventilated membrane and at this, electrochemical reaction (reduction) occurring, generates electronegative hydroxide ion (OH at this
-) dissolve in reaction electrolytic solution.In KCL in reaction electrolytic solution, most important composition is chloride, and chloride can isolate negative ion (Cl
-) each hydroxide ion (OH can be ensured
-) there is a chlorion (Cl
-) in silver, electrode (anode) is replaced, and generate insoluble silver chloride (AgCl).The electrode reaction relational expression that sensor enters water formation is as follows:
Working electrode (gold): O
2+ 2H
2o+4e
-→ 4OH
-
To electrode (silver): 4Ag+4Cl
-→ 4AgCl+4e
-
With the movement of electric charge between electrode, create the electric current of μ A level, trace dissolved oxygen tester is as measuring-signal and be converted into oxygen concentration, and its approximate reaction equation is:
O
2+4Ag+4Cl
-+2H
2O→4AgCl+4OH
-
In whole process, in reaction electrolytic solution, positive ion moves to negative pole, and negative ion moves to positive pole, by the migration between ion, forms electric current, thus complete loop in reaction electrolytic solution.
Nanoporous sensor provided by the invention, it is put by sensor to polarize 30 minutes in atmosphere that the saturated oxygen of the polarographic oxygen electrode that adopted (comprise golden working electrode and silver to electrode) is demarcated, reading is saturated oxygen value, tests and gets its mean value 30 times." zero " oxygen value is demarcated: the electrode polarized 2 hours, be placed in air, measure the numerical value of saturated oxygen, then electrode is placed in zero oxygen water (5g anhydrous sodium sulfite is dissolved in 100ml high purity water and obtains zero oxygen water) 30 minutes, after stable, test gets its mean value 30 times.
The reaction velocity test of nanoporous sensor provided by the invention puts into " zero " oxygen water after being polarized in atmosphere by sensor 2 hours, when the oxygen dissolving value shown is lower than 3ug/L, records the time used.Test gets its mean value 30 times altogether.
The aftercurrent test of nanoporous sensor provided by the invention puts into " zero " oxygen water after being polarized in atmosphere by sensor 2 hours after 72 hours, the current value of record sensor.Electric current is now aftercurrent, and test gets its mean value 30 times altogether.
Device of the present invention is not limited to the embodiment described in embodiment, and those skilled in the art's technical scheme according to the present invention draws and other embodiment belongs to technological innovation scope of the present invention equally.
Claims (9)
1. a nanoporous sensor, comprise sensor main body (7), oxygen permeation membrane (2), be arranged on the push rod (5) in the reaction chamber (14) in described sensor main body (7) and base (12), be arranged on working electrode (4) on described push rod (5) and to electrode (6), described working electrode (4) and to electrode (6) all by lead-in wire connecting electrode joint (13), reaction electrolytic solution is filled in described reaction chamber (14), it is characterized in that: the reaction surface of described working electrode (4) is porous structure, the diameter in hole is 60-100nm.
2. a kind of nanoporous sensor as claimed in claim 1, is characterized in that: the golden cylindrical shell of described working electrode (4) to be one end be shape for hat reaction surface.
3. a kind of nanoporous sensor as claimed in claim 1, is characterized in that: described is solenoid type filamentary silver to electrode (6).
4. a kind of nanoporous sensor as claimed in claim 1, is characterized in that: described oxygen permeation membrane (2) is fastened on described sensor main body (7) front end by body cover (3).
5. the preparation method of a kind of nanoporous sensor as described in any one of claim 1-4, comprises the steps:
A () prepares sensor main body, push rod, base, body cover and oxygen permeation membrane;
B () makes working electrode, working electrode reaction surface is carried out polishing and clean, and adopt electrochemical alloy-go alloyage to process described reaction surface, the reaction surface after process presents porous structure, and the diameter in hole is 60-100nm; Working electrode after process is placed in push rod top, the hollow-core construction of the lead-in wire in working electrode by push rod and base is drawn;
C () makes electrode, will carry out tempering and grinding process to electrode, outside around push rod to electrode retaining collar by after process, is drawn to the lead-in wire of electrode by the hollow-core construction of push rod and base;
D () will be assembled with working electrode, be fixed in the reaction chamber of sensor main body inside, by working electrode and the electrode contact to the lead-in wire connecting sensor of electrode to the push rod of electrode and base;
(e) ready reaction electrolytic solution, and be filled in the reaction chamber in sensor main body, by body cover, oxygen permeation membrane is arranged on sensor front end.
6. the preparation method of a kind of nanoporous sensor as claimed in claim 5, is characterized in that: in step (a), and described sensor main body, body cover, base adopt polyoxymethylene to make, and described oxygen permeation membrane, push rod adopt teflon to make.
7. the preparation method of a kind of nanoporous sensor as claimed in claim 5, it is characterized in that: in step (b), prepare a golden cylinder, be processed into the Cylinder Shell that one end is shape for hat reaction surface, polishing cleaning is carried out to described shape for hat reaction surface, and adopt electrochemical alloy-go alloyage to process described reaction surface, golden Cylinder Shell is embedded push rod top, and lead-in wire is drawn by the hollow-core construction of push rod and base in golden Cylinder Shell, working electrode completes.
8. the preparation method of a kind of nanoporous sensor as claimed in claim 5, it is characterized in that: in step (c), prepare a filamentary silver, tempering and grinding process are carried out to described filamentary silver, filamentary silver is looped around push rod periphery, described filamentary silver one end arranges lead-in wire, and draws lead-in wire by the hollow-core construction of push rod and base, completes electrode fabrication.
9. the preparation method of a kind of nanoporous sensor as claimed in claim 5, is characterized in that: in step (e), and described reaction electrolytic solution is potassium chloride and potassium hydroxide mixed liquor.
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