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WO2013081443A1 - Électrode sélective pour l'ammonium et procédé pour sa préparation - Google Patents

Électrode sélective pour l'ammonium et procédé pour sa préparation Download PDF

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Publication number
WO2013081443A1
WO2013081443A1 PCT/MY2012/000182 MY2012000182W WO2013081443A1 WO 2013081443 A1 WO2013081443 A1 WO 2013081443A1 MY 2012000182 W MY2012000182 W MY 2012000182W WO 2013081443 A1 WO2013081443 A1 WO 2013081443A1
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WO
WIPO (PCT)
Prior art keywords
sensor
transducer
ammonium
layer
polythiophene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/MY2012/000182
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English (en)
Inventor
Alva Sagir
Ahmad Mohd Rais
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mimos Bhd
Original Assignee
Mimos Bhd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mimos Bhd filed Critical Mimos Bhd
Publication of WO2013081443A1 publication Critical patent/WO2013081443A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/333—Ion-selective electrodes or membranes

Definitions

  • the present invention relates generally to compound detection device and methods, and more particularly to ammonia detection device and methods.
  • Nessler method Another example is the known Nessler method, which is also capable to detect ammonium ion but with spectrometry method, few sample pre-treatment steps need to be done before it and it will bring disadvantage in term of time consuming. Nessler method also has limitation over the level of turbidity of sample, since cloudy sample might not be able to analyze accurately. Moreover, the quick measurement needs to be done since the sample might easily change color.
  • polymer In view of potentiometric chemical sensor, polymer has become a useful element as it has capability of conducting electricity and at the same time able to function as transducer too.
  • the common polymers use for this particular purpose includes polyaniline, polythiophene, polypyrrole and polyacetylene . Nevertheless, an apparent problem related to using polymer is the potential of chemical reactions which leads to prohibition of electron transfer and thus the electrode become unstable.
  • this proposed sub-ppm ammonium ion sensor will overcome this indirect measurement because it provides a sensing element which can straight forward measure the ammonium concentration in liquid form.
  • the proposed ammonium sensor comprises of ammonium membrane on novel polythiophene transducer, which gives good accuracy at sub-ppm for aquaculture, environmental monitoring and medical applications.
  • This proposed sub-ppm ammonium ion sensor also has a simple measurement method because this sensor element is only need to be couple with a reference electrode and connect to a high impedance potential measuring device.
  • an ammonium ion sensor with cast doped polythiophene nanocomposite transducer comprising: a substrate; for providing mechanical strength for the sensor tip; at least one silver layer as conducting layer and wire trace; at least one carbon layer; to provide adhesion to cast polythiophene nanocomposite; at least one polythiophene transducer layer for converting chemical potential to electrical signal; and at least one ammonium sensing membrane for recognizing ammonium ion and transport it to the surface of the transducer layer.
  • a method of preparing the sub-ppm ammonium ion sensor with cast doped polythiophene nanocomposite transducer comprising the steps of: depositing carbon electrode, preferably via screen printing method; preparing CNT-polythiophenes conducting layer by chemical; drop coat polythiophenes on carbon electrode surface as transducer layer to allow electron transfer; characterizing CNT-polythiopene transducer; depositing ammonium ion membrane on polythiophenes transducer layer; and characterizing the ammonium ion sensor.
  • FIG 1 shows the sensor in accordance with one embodiment of the present invention
  • FIG 2 shows the steps involved in preparing a component in accordance with one embodiment of the present invention
  • FIG 3 shows an example of the sensor in accordance with an embodiment of the present invention
  • FIG 4 shows the results obtained based on the sensor in accordance with an embodiment of the present invention.
  • the present invention provides an ammonium sensor, which capable of doing trace level measurement in sub-ppm value.
  • This proposed ammonium sensor comprises of ammonium membrane on novel polythiophene transducer, which gives good accuracy at sub-ppm for aquaculture, environmental monitoring and medical applications.
  • This proposed ammonium ion sensors have a recognition element (ammonium selective membrane layer) which selectively picks the wanted chemical ion/ species and transducer (polythiophene layer) will convert the signal into an electronic signal and later the concentration of ion/species will be known.
  • the sub-ppm ammonium ion sensor with cast doped polythiophene nanocomposite transducer in accordance with the preferred embodiments of the present invention comprises: a substrate; for providing mechanical strength for the sensor tip; at least one silver layer as conducting layer and wire trace; at least one carbon layer; to provide adhesion to cast polythiophene nanocomposite; at least one polythiophene transducer layer for converting chemical potential to electrical signal; and at least one ammonium sensing membrane for recognizing ammonium ion and transport it to the surface of the transducer layer.
  • the steps involved in preparing the ammonium selective material with polythiophenes transducer membrane in accordance with one embodiment of the present invention includes: preparation of carbon electrode, preferably via screen printing method; preparation of CNT-polythiophenes conducting layer by chemical; coating polythiophenes on carbon electrode surface as transducer layer to allow electron transfer; characterizing CNT- polythiophene transducer; depositing an amount of, preferably 30 ⁇ 1 ammonium ion membrane of polythiophenes transducer layer; and characterization of ammonium ion sensor.
  • This portion of toxic and non toxic ammonia depends on water's temperature and pH condition. If the pH of water increases, the ammonia is converted to the un-ionized form of NH3. The non toxic form of NH4+ normally formed in the low pH or acidic conditions.
  • this proposed sub-ppm ammonium ion sensor also has a simple measurement method because this sensor element is adapted to be coupled only with a reference electrode and connect to high impedance potential measuring device.
  • the potentiometric sensor will have a potential variation depend on the concentration of ammonium ions in the solution.
  • This potential measuring device will measure a differential potential between sensing membrane surface with the potential generated by reference electrode. The potential different is measured as a voltage (mV) and plotted as a function of logarithmic ammonium concentration.
  • the doped polythiophene transducer of the sensor comprises 0.1 to 20% polythiophene', 0.1 to 20% dopant, 40 to 90% binder and 0.1 to 20% carbon nanotubes, all by weight.
  • R 2 H, methyl, methoxy, thiomethyl
  • R 3 H, methyl, ethyl, butyl, pentyl, hexyl, heptyl, octyl
  • the dopant of the sensor is at least one or combination of the following dopants; chloride, tetrafluoroborate, iodide, para-toluene sulfonate, trifluoromethane sulfonate, camphor sulfonate, poly styrene sulfonate, nafion, hexafluorophosphate .
  • dopants chloride, tetrafluoroborate, iodide, para-toluene sulfonate, trifluoromethane sulfonate, camphor sulfonate, poly styrene sulfonate, nafion, hexafluorophosphate .
  • Silver and carbon was screen printed on the printed circuit board substrate.
  • This SPE screen printed electrode
  • DI water to remove any dirt particle on the carbon surface which might affect the sensing performance later on.
  • the carbon printed electrode was cleaned and dried.
  • 10 microL polythiophene solution was carefully deposited on the carbon printed electrode by mean of drop casting. During this preparation, the polythiophene solution should be evenly spread on to the carbon surface area. Then, the electrode was allowed to dry for 30-45 minutes under a continuous flow of Nitrogen gas. The polythiophene layer should be dried before deposit another layer called membrane layer .
  • a cocktail for ammonium membrane layer was prepared by mixing of lmg potassium tetrakis p-chlorophenyl borate (KTpCIPB) , 3mg Ammonium Ionophore 1, 30mg high molecular weight of polyvinyl chloride (PVC) , and 3mg dioctyl sebacate (DOS) in a lOmL glass bottle.
  • the cocktail mixture was dissolved in lmL tetrahydrofuran (THF) and mixed homogeneously. Then, 30microL of cocktail membrane was drop-casting on the polythiophene layer and allowed to dry at room temperature for overnight.
  • the electrode was rinsed with DI water and conditioned in 10 "3 M of NH 4 C1 before characterization process.
  • the sub-ppm Ammonium Sensor prepared as above example is used as ammonium sensing electrode and paired with standard Ag/AgCl reference electrode, which were set-up with Orion Ion Meter.
  • the Ag/AgCl reference electrode was prepared 0.1M LiOAc (lithium acetate) as external electrolyte. After conditioning with 10 "3 M of NH 4 C1, the sensor electrode was rinsed with DI water and dried. The characterization was carried out in temperature of 25°C.
  • the standard test solution was prepared from a stock solution of 10 " 3 M NH 4 CI.
  • the NH4 + solution with concentration of 10 ⁇ 5 , 10 "6 and 10 " M for this experiment was prepared by dilution of stock solution with DI water.
  • the NH4+ solution is prepared in 0.18, 0.018 and 0.0018ppm value. This range of sub-ppm value of ammonium ion is applicable for environmental monitoring application.
  • this proposed sub-ppm ammonium sensor electrode shows Nernstian response of 58.03mV/decade over a range of
  • FIG 4 shows the results obtained based on the sensor of the present invention .

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)

Abstract

L'invention concerne un capteur d'ions ammonium sous-ppm avec transducteur nano-composite en polythiophène dopé par moulage comportant : un substrat servant à conférer une résistance mécanique à la pointe du capteur; au moins une couche d'argent en tant que couche conductrice et tracé de câblage; au moins une couche de carbone servant à assurer l'adhérence à un nano-composite en polythiophène moulé; au moins une couche de transducteur en polythiophène servant à convertir un potentiel chimique en signal électrique; et au moins une membrane de détection d'ammonium servant à reconnaître un ion ammonium et le transporter jusqu'à la surface de la couche de transducteur.
PCT/MY2012/000182 2011-12-02 2012-06-29 Électrode sélective pour l'ammonium et procédé pour sa préparation Ceased WO2013081443A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2011005854 2011-12-02
MYPI2011005854 2011-12-02

Publications (1)

Publication Number Publication Date
WO2013081443A1 true WO2013081443A1 (fr) 2013-06-06

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI625522B (zh) * 2016-10-17 2018-06-01 英屬開曼群島商通潤股份有限公司 平面型氨選擇性感測電極及其製法
CN108732217A (zh) * 2018-04-28 2018-11-02 深圳市西尔曼科技有限公司 铵离子微电极及其制作方法
US10473610B2 (en) 2016-10-17 2019-11-12 Akubic (Cayman) Limited Planar ammonia selective sensing electrode and manufacturing method thereof
CN115856035A (zh) * 2022-11-16 2023-03-28 南方科技大学 一种铵离子传感器及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010091475A1 (fr) * 2009-02-13 2010-08-19 Curtin University Of Technology Dispositif et procédé de détection

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010091475A1 (fr) * 2009-02-13 2010-08-19 Curtin University Of Technology Dispositif et procédé de détection

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
AMERICAN CHEMICAL SOCIETY: "ACS National Exposition - DropSens", vol. 242, 29 August 2011 (2011-08-29), Denver, USA, XP002690430, Retrieved from the Internet <URL:https://acs.expoplanner.com/index.cfm?fuseaction=expomap.exhib&event_id=1040&exhib_id=3597> [retrieved on 20130116] *
DROPSENS: "DropSens Catalogue 2011", March 2011 (2011-03-01), XP002690429, Retrieved from the Internet <URL:http://www.dropsens.co.uk/Downloads/DropSens_Catalogue.pdf> [retrieved on 20130116] *
GHAURI M S ET AL: "EVALUATION OF AN AMMONIUM IONOPHORE FOR USE IN POLY(VINYL CHLORIDE) MEMBRANE ION-SELECTIVE ELECTRODES: SOLVENT MEDIATOR EFFECTS", ANALYST, LONDON, GB, vol. 119, 1 November 1994 (1994-11-01), pages 2323 - 2326, XP002952138, DOI: 10.1039/AN9941902323 *
MOUSAVI Z ET AL: "Poly(3,4-ethylenedioxythiophene) (PEDOT) doped with carbon nanotubes as ion-to-electron transducer in polymer membrane-based potassium ion-selective electrodes", JOURNAL OF ELECTROANALYTICAL CHEMISTRY AND INTERFACIAL ELECTRO CHEMISTRY, ELSEVIER, AMSTERDAM, NL, vol. 633, no. 1, 1 August 2009 (2009-08-01), pages 246 - 252, XP026349168, ISSN: 0022-0728, [retrieved on 20090613] *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI625522B (zh) * 2016-10-17 2018-06-01 英屬開曼群島商通潤股份有限公司 平面型氨選擇性感測電極及其製法
US10473610B2 (en) 2016-10-17 2019-11-12 Akubic (Cayman) Limited Planar ammonia selective sensing electrode and manufacturing method thereof
CN108732217A (zh) * 2018-04-28 2018-11-02 深圳市西尔曼科技有限公司 铵离子微电极及其制作方法
CN115856035A (zh) * 2022-11-16 2023-03-28 南方科技大学 一种铵离子传感器及其制备方法

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