CN101858882A - Nitrate ion selective electrode based on polypyrrole film and preparation method thereof - Google Patents
Nitrate ion selective electrode based on polypyrrole film and preparation method thereof Download PDFInfo
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- CN101858882A CN101858882A CN 201010135367 CN201010135367A CN101858882A CN 101858882 A CN101858882 A CN 101858882A CN 201010135367 CN201010135367 CN 201010135367 CN 201010135367 A CN201010135367 A CN 201010135367A CN 101858882 A CN101858882 A CN 101858882A
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 31
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 37
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 29
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 13
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims description 37
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 20
- 239000004593 Epoxy Substances 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 150000003233 pyrroles Chemical class 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 3
- 150000002118 epoxides Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 16
- 238000004458 analytical method Methods 0.000 abstract description 4
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- -1 Polytetrafluoroethylene Polymers 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 229910021397 glassy carbon Inorganic materials 0.000 abstract 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
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- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a nitrate ion selective electrode based on a polypyrrole film. The nitrate ion selective electrode is characterized in that a glassy carbon rod is mounted at the bottom of a cylindrical PTFE (Polytetrafluoroethylene) sleeve, a copper rod is arranged in the PTFE sleeve, and a nitrate ion-doped polypyrrole film is arranged on the lower surface of the glassy carbon rod, wherein the upper surface of the glassy carbon rod is connected with the copper rod and an outgoing lead is arranged at the upper end of the copper rod. The preparation method comprises the following steps of: (1) removing an oxide layer on the surface of the glassy carbon rod and embedding the glassy carbon rod in the bottom of the PTFE sleeve; (2) mounting the copper rod in the PTFE sleeve and connecting and making the outgoing lead at the upper end of the copper rod into an electrode; (3) plating, polymerizing and coating the lower surface of the glassy carbon rod in a mixed solution of a pyrrole solution and a sodium nitrate solution; and (4) activating the electrode plated with a sensing film in the sodium nitrate solution. The nitrate ion selective electrode has the advantages of favorable stability, reproducibility, selectivity, long service life, and the like and can be widely applied to the analysis and the determination of nitrate ion concentration.
Description
Technical field
The present invention relates to the film modified electrode of a kind of polypyrrole (Ppy), especially a kind of nitrate ion selective electrode based on nitrate radical polypyrrole (Ppy) modified membrane and preparation method thereof.
Background technology
Along with increasing the weight of day by day of body eutrophication, in the water quality total nitrogen, total phosphorus remove and monitor the important topic that becomes current environmental protection, total nitrogen is one of important indicator of judging surface water, potable water and pollution of waterhead degree.It is fast that analysis with ion selective electrodes has response speed, is not subject to solution colour and sedimentary influence, is particularly suitable for water quality automatic monitor for continuously and on-the site analysis.Electric polypyrrole has favorable conductive character to be made it to be easier to be prepared into ion-sensitive electron device and biological electronics device and obtains paying close attention to.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and have good stability, reappearance and optionally based on nitrate ion selective electrode of polypyrrole film and preparation method thereof.
According to technical scheme provided by the invention, described nitrate ion selective electrode based on polypyrrole film, feature is: adopt at the PTFE of cylindricality (teflon) sleeve bottom the glass carbon-point is installed, inside at the PTFE sleeve pipe is provided with copper rod, lower surface at the glass carbon-point is provided with one deck doping nitrate radical film of poly pyrrole, the upper surface of described glass carbon-point links to each other with copper rod, in the copper rod upper end extension line is set.
Utilize epoxy sealing between described PTFE sleeve pipe and glass carbon-point and the copper rod.
A kind of preparation method of the nitrate ion selective electrode based on polypyrrole film, described method comprises the steps:
(1) with sand papering glass carbon-point surface, removes the oxide layer on glass carbon-point surface; The glass carbon-point is embedded the bottom of PTFE sleeve pipe, and use epoxy sealing;
(2) in the PTFE sleeve pipe, copper rod is installed, is compressed between copper rod and the glass carbon-point, use epoxy sealing between copper rod upper end and the PTFE sleeve pipe, connect extension line in the upper end of copper rod and make electrode;
(3) film of poly pyrrole of plating polymerization doping nitrate radical: carbon-point, spun gold, filamentary silver or platinum group metal silk are connected with power cathode, the extension line of electrode is connected with the anode of power supply, negative electrode and anode are immersed in the film of poly pyrrole of electroplating one deck doping nitrate radical in the polymer solution at the lower surface of glass carbon-point, electric current is 0.1～0.25mA in the plating polymerization process, and electricity end polymerization time is 10～30min; Described polymer solution is the sodium nitrate that adds pyrroles and the 0.005～0.01mol of 0.005～0.01mol in the deionized water of 100～150ml;
(4) activation: will electroplate electrode behind the film of poly pyrrole of polymerization doping nitrate radical and in the sodium nitrate solution of 0.0005～0.001mol/L, soak and carry out activation processing, until the potential change of the electrode that records between 1～2mV.
Described epoxy resin is the epoxy resin of epoxide number 0.25～0.45.
Nitrate ion of the present invention selects electrode to have advantages such as good stable, reappearance, selectivity and long service life, can be widely used in the analysis and the mensuration of nitrate ion concentration.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is an electrodes selective performance standard curve map.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
As shown in Figure 1: electrodes selective comprises PTFE sleeve pipe 1, copper rod 2, glass carbon-point 3, doping nitrate radical film of poly pyrrole 4, extension line 5 etc.
The present invention adopts at the PTFE of cylindricality sleeve pipe 1 bottom installation glass carbon-point 3, in the inside of PTFE sleeve pipe 1 copper rod 2 is set, lower surface at glass carbon-point 3 is provided with one deck doping nitrate radical film of poly pyrrole 4, and the upper surface of described glass carbon-point 3 links to each other with copper rod 2, in copper rod 2 upper ends extension line 5 is set.
Platinum group metal used in the present invention silk comprises platinum (Pt), palladium (Pd), osmium (Os), iridium (Ir), ruthenium (Ru), six kinds of metals of rhodium (Rh).Employed epoxy resin is the epoxy resin of middle ring oxygen value 0.25～0.45, can be used as cementing agent and uses.
Embodiment one: a kind of preparation method of electrodes selective comprises the steps:
(1) with sand papering glass carbon-point surface, removes the oxide layer on glass carbon-point surface; The glass carbon-point is embedded the bottom of PTFE sleeve pipe, and use epoxy sealing;
(2) in the PTFE sleeve pipe, copper rod is installed, is compressed between copper rod and the glass carbon-point, use epoxy sealing between copper rod upper end and the PTFE sleeve pipe, connect extension line in the upper end of copper rod and make electrode;
(3) film of poly pyrrole of plating polymerization doping nitrate radical: carbon-point, spun gold, filamentary silver or platinum group metal silk are connected with power cathode, the extension line of electrode is connected with the anode of power supply, negative electrode and anode are immersed in the film of poly pyrrole of electroplating one deck doping nitrate radical in the polymer solution at the lower surface of glass carbon-point, electric current is 0.1mA in the plating polymerization process, and electricity end polymerization time is 30min; Described polymer solution is to add the pyrroles of 0.005mol and the sodium nitrate of 0.005mol in the deionized water of 100ml;
(4) activation: will electroplate electrode behind the film of poly pyrrole of polymerization doping nitrate radical and in the sodium nitrate solution of 0.0005mol/L, soak and carry out activation processing, until the potential change of the electrode that records between 1～2mV.
Embodiment two: a kind of preparation method of electrodes selective comprises the steps:
(1) with sand papering glass carbon-point surface, removes the oxide layer on glass carbon-point surface; The glass carbon-point is embedded the bottom of PTFE sleeve pipe, and use epoxy sealing;
(2) in the PTFE sleeve pipe, copper rod is installed, is compressed between copper rod and the glass carbon-point, use epoxy sealing between copper rod upper end and the PTFE sleeve pipe, connect extension line in the upper end of copper rod and make electrode;
(3) film of poly pyrrole of plating polymerization doping nitrate radical: carbon-point, spun gold, filamentary silver or platinum group metal silk are connected with power cathode, the extension line of electrode is connected with the anode of power supply, negative electrode and anode are immersed in the film of poly pyrrole of electroplating one deck doping nitrate radical in the polymer solution at the lower surface of glass carbon-point, electric current is 0.1mA in the plating polymerization process, and electricity end polymerization time is 10min; Described polymer solution is to add the pyrroles of 0.01mol and the sodium nitrate of 0.01mol in the deionized water of 150ml;
(4) activation: will electroplate electrode behind the film of poly pyrrole of polymerization doping nitrate radical and in the sodium nitrate solution of 0.001mol/L, soak and carry out activation processing, until the potential change of the electrode that records between 1～2mV.
Embodiment three: a kind of preparation method of electrodes selective comprises the steps:
(1) with sand papering glass carbon-point surface, removes the oxide layer on glass carbon-point surface; The glass carbon-point is embedded the bottom of PTFE sleeve pipe, and use epoxy sealing;
(2) in the PTFE sleeve pipe, copper rod is installed, is compressed between copper rod and the glass carbon-point, use epoxy sealing between copper rod upper end and the PTFE sleeve pipe, connect extension line in the upper end of copper rod and make electrode;
(3) film of poly pyrrole of plating polymerization doping nitrate radical: carbon-point, spun gold, filamentary silver or platinum group metal silk are connected with power cathode, the extension line of electrode is connected with the anode of power supply, negative electrode and anode are immersed in the film of poly pyrrole of electroplating one deck doping nitrate radical in the polymer solution at the lower surface of glass carbon-point, electric current is 0.18mA in the plating polymerization process, and electricity end polymerization time is 20min; Described polymer solution is to add the pyrroles of 0.008mol and the sodium nitrate of 0.008mol in the deionized water of 130ml;
(4) activation: will electroplate electrode behind the film of poly pyrrole of polymerization doping nitrate radical and in the sodium nitrate solution of 0.0008mol/L, soak and carry out activation processing, until the potential change of the electrode that records between 1～2mV.
Nitrate ion selective electrode of the present invention adopts calibration curve method, analyze the standard solution of a series of concentration of pure preparation with sodium nitrate, utilize the potential value of nitrate ion selective electrode bioassay standard solution respectively, in order to estimate the performance of nitrate ion selective electrode, the result as shown in Figure 2.The nitrate ion selective electrode of making, the thickness of its bottom sensitive membrane is 10～100 μ m, linear response range 10
-1～10
-5Mol/L, promptly electrode can be measured 10
-1～10
-5Nitrate ion in the mol/L concentration range, and magnitude of voltage and-log[NO
3 -] linear, the linear regression coeffficient slope is 45.449 ± 2.0mV/decade, is limited to 1 * 10 under the nitrate ion concentration of detection
-5Mol/L.Electrode response time of the present invention is short, is generally less than 30s, and volume is little, and preparation is simple, and cost is low.
Claims (4)
1. nitrate ion selective electrode based on polypyrrole film, it is characterized in that: adopt in the PTFE of cylindricality sleeve pipe (1) bottom glass carbon-point (3) is installed, in the inside of PTFE sleeve pipe (1) copper rod (2) is set, lower surface at glass carbon-point (3) is provided with one deck doping nitrate radical film of poly pyrrole (4), the upper surface of described glass carbon-point (3) links to each other with copper rod (2), in copper rod (2) upper end extension line (5) is set.
2. electrodes selective as claimed in claim 1 is characterized in that: utilize epoxy sealing between described PTFE sleeve pipe (1) and glass carbon-point (3) and the copper rod (2).
3. the preparation method based on the nitrate ion selective electrode of polypyrrole film is characterized in that, described method comprises the steps:
(1) with sand papering glass carbon-point surface, removes the oxide layer on glass carbon-point surface; The glass carbon-point is embedded the bottom of PTFE sleeve pipe, and use epoxy sealing;
(2) in the PTFE sleeve pipe, copper rod is installed, is compressed between copper rod and the glass carbon-point, use epoxy sealing between copper rod upper end and the PTFE sleeve pipe, connect extension line in the upper end of copper rod and make electrode;
(3) film of poly pyrrole of plating polymerization doping nitrate radical: carbon-point, spun gold, filamentary silver or platinum group metal silk are connected with power cathode, the extension line of electrode is connected with the anode of power supply, negative electrode and anode are immersed in the film of poly pyrrole of electroplating one deck doping nitrate radical in the polymer solution at the lower surface of glass carbon-point, electric current is 0.1～0.25mA in the plating polymerization process, and electricity end polymerization time is 10～30min; Described polymer solution is the sodium nitrate that adds pyrroles and the 0.005～0.01mol of 0.005～0.01mol in the deionized water of 100～150ml;
(4) activation: will electroplate electrode behind the film of poly pyrrole of polymerization doping nitrate radical and in the sodium nitrate solution of 0.0005～0.001mol/L, soak and carry out activation processing, until the potential change of the electrode that records between 1～2mV.
4. preparation method as claimed in claim 3 is characterized in that: described epoxy resin is the epoxy resin of epoxide number 0.25～0.45.
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| CN 201010135367 CN101858882B (en) | 2010-03-17 | 2010-03-17 | Preparation method of nitrate ion selective electrode based on polypyrrole film |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102445468A (en) * | 2011-09-29 | 2012-05-09 | 重庆大学 | Electrode for determining nitrate concentration in solution and manufacturing method thereof |
| CN102645467A (en) * | 2012-03-08 | 2012-08-22 | 宁波大学 | Glassy carbon electrode complex integrated with electroacoustic double-excitation micromechanism in working end |
| CN102650610A (en) * | 2012-03-08 | 2012-08-29 | 宁波大学 | Glassy carbon electrode compactly combined with acoustic excitation mechanism in electrode stem |
| CN103293205A (en) * | 2013-06-08 | 2013-09-11 | 江南大学 | Preparation method of full-solid ion selective electrode based on bilayer membrane structure |
| CN103675068A (en) * | 2013-03-28 | 2014-03-26 | 浙江大学 | Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof |
| CN106018525A (en) * | 2016-05-20 | 2016-10-12 | 浙江刚竹网络科技有限公司 | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof |
| CN106353383A (en) * | 2016-10-10 | 2017-01-25 | 常州大学 | Sensor for detecting hexafluorophosphate ions |
| CN106480482A (en) * | 2016-12-15 | 2017-03-08 | 河海大学常州校区 | A kind of cathode surface nanosecond pulse plasma prepares solution and the preparation method of catalytic nanometer perforated membrane |
| CN113176318A (en) * | 2021-04-26 | 2021-07-27 | 东南大学 | Double-layer film solid phosphate ion selective electrode and preparation method thereof |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102445468B (en) * | 2011-09-29 | 2013-01-16 | 重庆大学 | Electrode for determining nitrate concentration in solution and manufacturing method thereof |
| CN102445468A (en) * | 2011-09-29 | 2012-05-09 | 重庆大学 | Electrode for determining nitrate concentration in solution and manufacturing method thereof |
| CN102650610B (en) * | 2012-03-08 | 2016-05-11 | 宁波大学 | The inner compactness of electrode stem combines the glass-carbon electrode of microminiature acoustically-driven mechanism |
| CN102645467A (en) * | 2012-03-08 | 2012-08-22 | 宁波大学 | Glassy carbon electrode complex integrated with electroacoustic double-excitation micromechanism in working end |
| CN102650610A (en) * | 2012-03-08 | 2012-08-29 | 宁波大学 | Glassy carbon electrode compactly combined with acoustic excitation mechanism in electrode stem |
| CN102645467B (en) * | 2012-03-08 | 2016-05-11 | 宁波大学 | Working end is inner integrated electricity, the two glass-carbon electrode synthesis that encourages micro mechanism of sound |
| CN103675068A (en) * | 2013-03-28 | 2014-03-26 | 浙江大学 | Bismuth nitrate oxide based solid nitrate electrode and preparation method thereof |
| CN103675068B (en) * | 2013-03-28 | 2015-10-21 | 浙江大学 | A kind of solid nitric acid root electrode based on nitric acid oxidation bismuth and preparation method thereof |
| CN103293205A (en) * | 2013-06-08 | 2013-09-11 | 江南大学 | Preparation method of full-solid ion selective electrode based on bilayer membrane structure |
| CN103293205B (en) * | 2013-06-08 | 2015-09-23 | 江南大学 | Based on the preparation method of all solid state ion-selective electrode of double membrane structure |
| CN106018525A (en) * | 2016-05-20 | 2016-10-12 | 浙江刚竹网络科技有限公司 | High sensitivity lead ion electrode based on polypyrrole and preparation method thereof |
| CN106353383A (en) * | 2016-10-10 | 2017-01-25 | 常州大学 | Sensor for detecting hexafluorophosphate ions |
| CN106353383B (en) * | 2016-10-10 | 2019-05-28 | 常州大学 | A kind of sensor detecting hexafluorophosphoricacid acid ions |
| CN106480482A (en) * | 2016-12-15 | 2017-03-08 | 河海大学常州校区 | A kind of cathode surface nanosecond pulse plasma prepares solution and the preparation method of catalytic nanometer perforated membrane |
| CN113176318A (en) * | 2021-04-26 | 2021-07-27 | 东南大学 | Double-layer film solid phosphate ion selective electrode and preparation method thereof |
| CN113176318B (en) * | 2021-04-26 | 2023-10-27 | 东南大学 | Double-layer film solid phosphate ion selective electrode and preparation method thereof |
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