WO2012064179A1 - Capteur de ph - Google Patents

Capteur de ph Download PDF

Info

Publication number
WO2012064179A1
WO2012064179A1 PCT/MY2011/000135 MY2011000135W WO2012064179A1 WO 2012064179 A1 WO2012064179 A1 WO 2012064179A1 MY 2011000135 W MY2011000135 W MY 2011000135W WO 2012064179 A1 WO2012064179 A1 WO 2012064179A1
Authority
WO
WIPO (PCT)
Prior art keywords
sensor
doped
depositing
layer
polypyrrole
Prior art date
Application number
PCT/MY2011/000135
Other languages
English (en)
Inventor
Ahmad Mohd Rais
Alva Sagir
Original Assignee
Mimos Berhad
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 Berhad filed Critical Mimos Berhad
Publication of WO2012064179A1 publication Critical patent/WO2012064179A1/fr

Links

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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B7/00—Electrophoretic production of compounds or non-metals

Definitions

  • the present invention relates to an improved pH sensor for electrochemical sensing and method of preparing the same .
  • PVC chloride
  • silver-silver chloride (Ag/AgCl) electrode has been employed as the electrochemical transducer in chemical sensors and reference electrode. While the Ag/ AgCl electrode works best in the bulky glass electrode equipped with comparatively large volume of liquid internal electrolyte, the miniaturized solid state version employs hydrophilic polymeric membrane as an internal layer. In a typical laboratory procedure, the internal layer is hydrated with certain concentration of the target analyte, to act as the reference concentration. Depending on storage condition and due to other factors like aging the concentration of the internal layer changes and thus causes the electrical signal to change. This requires frequent or daily calibration; else the sensor would transmit inaccurate data.
  • Ag/AgCl silver-silver chloride
  • Polypyrole has been the most widely used due to numerous advantages. Doping the polypyrrole increases the conductivity of the conducting polymer and this is usually achieved by electropolymerization from solution of pyrrole monomer containing electrolyte of chloride or nitrate salts of potassium. This causes a problem because the doping electrolyte is aqueous solution, whereas the pyrrole monomer is only moderately soluble in this electrolyte. Therefore, vigorous shaking and continous stirring are required to achieve homogenous mixture and to maintain homogeneity of the doped polypyrrole on a pH sensor.
  • polypyrole layer 14 comprising; a substrate 18, a thick film screen printed carbon layer 16, a pH sensing membrane 12; polypyrole layer 14; characterized in that the polypyrole layer 14 is homogeneously doped on the carbon layer 16.
  • X CI, Br, I, BF 4 , PF 6 , OAc, CF 3 C0 2 , N0 3 , Fe(CN) 6 , oxalate, tosylate
  • n 1, 2, 3
  • R H, methyl, ethyl, butyl, allyl
  • the pH sensing membrane 12 is photo-cured co-polymer of methyl methacrylate and tetrahydrofurfuryl acrylate containing photoinitiator, diacrylate crosslinker, lipophilic borate salt and hydrogen ionophore.
  • the pH sensing membrane 12 is bulk co-polymer of methyl
  • methacrylate and tetrahydrofurfuryl acrylate containing photoinitiator, diacrylate crosslinker, lipophilic borate salt and hydrogen ionophore are examples of photoinitiator, diacrylate crosslinker, lipophilic borate salt and hydrogen ionophore.
  • ISE electrode
  • step (a) the pyrrole monomer doped electrolyte solution having concentration ranges from 0.1M to 3M of pyrrole monomer and the hydrophilic dopant in a polar solvent having a concentration ranges from 0.1M to 3M.
  • the hydrophilic dopant is choline chloride.
  • the depositing step (c) is by electrochemical polymerization of constant current method with current density of 0.1 to 10 mA per square centimetre.
  • the depositing step (c) is by electrochemical polymerization utilising cyclic voltammetry method with scans between - IV and +1V.
  • transducer layer increases the potential of obtaining homogeneously doped polypyrrole layer on the pH sensor.
  • the preparation of the pH sensor takes shorter time by utilising the method of depositing doped polypyrrole electrochemical transducer layer.
  • Figure 1 illustrates pH Sensor with doped polypyrrole
  • Figure 2 iillustrates hydrophilic organic salts for polypyrrole doping
  • Figure 3 illustrates doped polypyrrole conducting polymer.
  • Figure 4 illustrates molecular structures of methyl methacrylate (2) and tetrahydrofurfuryl acrylate (3) monomers
  • Figure 5 illustrates cyclic voltammatograms of Ppy(Cl) from ethanol solvent on Pt in 0.1M KC1 with 90 and 150 sec electropolymerisation time.
  • Figure 7 illustrates cyclic voltammatograms of Ppy(Cl) from 50% ethanol solvent on Pt in 0.1M KCl with 0.5, 1, 1.5, 2, 3, 4 and 5 mA cm 2 electropolymerisation current density.
  • Figure 8 illustrates pH sensor response (50% v/v ethanol platform) with various electropolymerisation current densities.
  • Figure 9 illustrates cyclic voltammatograms of Ppy(Cl) from 25% ethanol solvent on Pt in 0.1M KCl with 1, 2, 3, 4 and 5 mA cnr 2 electropolymerisation current density.
  • Figure 10 illustrates pH sensor response (25% v/v ethanol platform) with various electropolymerisation current densities.
  • Figure 11 illustrates plot of response versus Hydrogen Ion Activity for MT28 pH
  • the present invention relates to a miniaturized solid state pH sensor as illustrated in Figure 1 based on doped polypyrrole wherein the doping electrolytes are hydrophilic organic saltsl as illustrated in Figure 2 dissolved in polar organic solvent, mixture of polar solvents or mixture of polar solvent and deionized water.
  • the miniaturized solid state pH sensor 10 based on doped polypyrrole electrochemical transducer that gives stable electrical signal.
  • the pH sensor 10 does not require the use of hydrophilic internal layer and is easy to fabricate.
  • FIG. 1 shows a pH sensor 10 comprising; a substrate 18, a thick film screen
  • FIG. 1 also shows that the polypyrrole conducting polymer 14 is deposited on top of screen printed thick film carbon 16 electrode. The carbon 16 surface must first be cleaned by sonication, and the pyrrole monomer is electropolymerized from the doping electrolyte.
  • the doped polypyrrole layer 14 having
  • X CI, Br, I, BF 4 , PF 6 , OAc, CF 3 C0 2 , N0 3 , Fe(CN) 6 , oxalate, tosylate
  • n l, 2, 3
  • the pH sensing membrane 12 is photo-cured co-polymer of methyl methacrylate and tetrahydrofurfuryl acrylate containing pho- toinitiator, diacrylate crosslinker, lipophilic borate salt and hydrogen ionophore.
  • the pH sensing membrane 12 is bulk copolymer of methyl methacrylate and tetrahydrofurfuryl acrylate containing pho- toinitiator, diacrylate crosslinker, lipophilic borate salt and hydrogen ionophore.
  • the pH sensor 10 of the present invention is usable in the manufacture of an ion selective electrode (ISE) pH sensing device. Also, the pH sensor 10 is usable in the manufacture of an ion sensitive field effect transistor (ISFET) pH sensing device.
  • ISE ion selective electrode
  • ISFET ion sensitive field effect transistor
  • the electrolytes of hydrophilic organic salts are prepared by dissolution in polar organic such as ethanol, methanol, 2-methoxy ethanol, dimethyl sulfoxide, acetonitrile or tetrahydrofuran. Mixture of polar organic solvents or mixture of the organic solvent and deionized water can also be used to dissolve the salts and the pyrrole monomer. Pyrrole exhibits very high solubility in these solvents and vigorous shaking or stirring is not required for mixing or in keeping homogeneity during electropolymerization.
  • polar organic such as ethanol, methanol, 2-methoxy ethanol, dimethyl sulfoxide, acetonitrile or tetrahydrofuran.
  • step (a) the pyrrole monomer doped electrolyte solution having concentration ranges from 0.1M to 3M of pyrrole monomer and the hydrophilic dopant in a polar solvent having a concentration ranges from 0.1M to 3M.
  • the hydrophilic dopant is choline chloride.
  • the depositing step (c) is by electrochemical polymerization of
  • the depositing step (c) is by electrochemical polymerization
  • Co-polymer of acrylates, methyl methacrylate (2) and tetrahydrofurfuryl acrylate (3) has been employed as the pH sensing membranes 12 based on doped polypyrrole.
  • the monomers can be photo-polymerized from a cocktail containing the monomers, pho- toinitiator, crosslinker, lipophilic borate salt and hydrogen ionophore.
  • bulk co-polymer of the above monomers can also be used as the sensing membrane 12.
  • the bulk co-polymer is first synthesized by refluxing the desired ratios of the monomers and benzoyl peroxide in benzene. After purification and drying, samples from the bulk polymer are dissolved with methylene chloride or tetrahydrofuran, along with the above components for pH sensing membrane 12. A few microliters of the bulk cocktail is dispensed coated on the sonicated polypyrrole electrode and the solvent air dried before testing for pH response can be conducted.
  • Polypyrole is a conducting polymer due to its conjugated network of double bonds.
  • Polypyrrole has another property that is of interest in chemical sensing - it undergoes reversible oxidation-reduction cycle at well-defined potentials. This property allows the use of polypyrrole as electrochemical transducer in chemical and biosensors.
  • transducer layer increases the potential of obtaining homogeneously doped polypyrrole layer on the pH sensor.
  • the preparation of the pH sensor takes shorter time by utilising the method of depositing doped polypyrrole electrochemical transducer layer.
  • the screen printed electrodes (SPE) with 4 mm diameter were cleaned ultrasonically with deionised water for 1 min.
  • the electrochemical polymerisation was performed in a conventional three-electrode cell with a Pt as counter electrode and the Ag/AgCl double junction as reference electrode using Autolab PGSTAT MODEL 128N for 90 and 150 sec.
  • the polypyrrole (Ppy) films were generated with current density of 2 mA cm- 2 in aqueous solution of 0.5M pyrrole containing 1M choline chloride dopant and 50% v/v ethanol solvent.
  • cyclic voltammetry experiments were conducted between -1.0 V and +1.0 V with a potential sweep rate of 100 mV sec 1 in 0.1M potassium chloride (KC1) solution. The plots were shown as illustrated in Figure 5.
  • pH cocktail 12 was prepared by mixing 37 mg poly(vinyl) chloride (PVC), 3 mg sodium tetrakis[bis-3,5(trifluoromethyl)phenyl] borate (NaTFPB), 10.6 mg Tridodecyl amine (Hydrogen Ionophore I), 67 mg Bis(2-Ethylhexyl) Sebacate (DOS) and 600 DL tetrahydofuran (THF) solvent. Then, the homogenous cocktail 12 was deposited on top of Ppy film 14 with 50% v/v ethanol as solvent formed on top of SPE and dried overnight at room temperature.
  • PVC poly(vinyl) chloride
  • NaTFPB sodium tetrakis[bis-3,5(trifluoromethyl)phenyl] borate
  • Tridodecyl amine Hydrogen Ionophore I
  • DOS Bis(2-Ethylhexyl) Sebacate
  • THF DL t
  • This pH sensor 10 was tested using commercial Ag/ AgCl double junction reference electrode with 0.1M LiOAc as outer solution. The results were shown in Table 1. The plots of emf response versus activity of hydrogen ion 9 have shown acceptable Nernstian response and linearity.
  • pH cocktail 12 was prepared follow by example 1. The homogenous cocktail 12 was deposited on top of Ppy film 14 with 50% v/v ethanol as solvent formed on top of each SPE with current density various and dried overnight at room temperature. This pH sensor 10 was tested using commercial Ag/AgCl double junction reference electrode with 0.1M LiOAc as outer solution. The results were shown in Table 2. The plots of emf response versus activity of hydrogen ion 11 have shown acceptable Nernstian response and linearity.
  • the screen printed electrodes (SPE) with 4 mm diameter were cleaned ultrasonically with deionised water for 1 min.
  • the electrochemical polymerisation was performed in a conventional three-electrode cell with a Pt as counter electrode and the Ag/AgCl double junction as reference electrode using Autolab PGSTAT MODEL 128N for 90 sec.
  • the polypyrrole (Ppy) films were generated with current density of 1, 2, 3, 4 and 5 mA cm 2 in aqueous solution of 0.5M pyrrole containing 1M choline chloride dopant and 25% v/v ethanol solvent.
  • cyclic voltammetry experiments were conducted between -1.0 V and +0.4 V with a potential sweep rate of 100 mV sec 1 in 0.1M potassium chloride (KC1) solution. The plots were shown as Figure 9.
  • pH cocktail 12 was prepared follow by example 1. The homogenous cocktail was deposited on top of Ppy film 14 with 25% v/v ethanol as solvent formed on top of each SPE with current density various and dried overnight at room temperature. This pH sensor 10 was tested using commercial Ag/AgCl double junction reference electrode with 0.1M LiOAc as outer solution. The results were shown in Table 3. The plots of emf response versus activity of hydrogen ion 13 have shown acceptable Nernstian response and linearity.
  • MT28 cocktail (lOOuL) was first prepared by mixing 2 parts of methyl methacrylate monomer and 8 parts of tetrahydrofurfuryl acrylate monomer - by volume. The MT28 cocktail was transferred into a 5mL vial and lmg
  • the MT28 pH cocktail (luL) 12 was dispensed over the freshly fabricated polypyrrole-carbon electrode covered by thin layer of PVC film containing the pH sensing components.
  • the PVC layer acts as an interface layer that helps cover the porous polypyrrole layer 14.
  • the PVC interface layer was prepared using solvent cast technique using high molecular weight PVC.
  • the dispensed MT28 cocktail 12 was photocured under UV radiation in nitrogen ambient for 180sec.
  • the MT28 pH sensor 10 was characterized for response to hydrogen ion at pH 4, 7 and 10 (Table 4). The plot of the pH response is provided in Figure 11.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

La présente invention concerne un capteur de pH amélioré (10) pour la détection électrochimique et son procédé de préparation. Le capteur de pH (10) ayant pour base un transducteur électrochimique de polypyrrole dopé délivre un signal électrique stable. Le capteur de pH (10) ne nécessite pas l'utilisation d'une couche interne hydrophile et est facile à fabriquer.
PCT/MY2011/000135 2010-11-12 2011-06-23 Capteur de ph WO2012064179A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MYPI2010005312 2010-11-12
MYPI2010005312 2010-11-12

Publications (1)

Publication Number Publication Date
WO2012064179A1 true WO2012064179A1 (fr) 2012-05-18

Family

ID=46051155

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/MY2011/000135 WO2012064179A1 (fr) 2010-11-12 2011-06-23 Capteur de ph

Country Status (1)

Country Link
WO (1) WO2012064179A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9763605B2 (en) 2013-11-27 2017-09-19 Verily Life Sciences Llc Adjustment of sensor sensitivity by controlling copolymer film thickness through a controlled drying step
CN110243899A (zh) * 2019-07-15 2019-09-17 辽宁大学 一种pH敏感石墨烯纳米复合材料及其制备方法和应用
CN111307911A (zh) * 2018-12-11 2020-06-19 有研工程技术研究院有限公司 一种pH传感器及其制备方法
CN113063995A (zh) * 2021-03-16 2021-07-02 中国海洋大学 一种碳基导电聚合物膜水下电场传感器
CN113500189A (zh) * 2021-08-10 2021-10-15 复旦大学 一种锌微球-聚吡咯可降解复合材料及其界面超组装制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5605617A (en) * 1993-03-29 1997-02-25 Commissariat A L'energie Atomique Conductive polymer film doped by mixed heteropolyanions usable for the detection of nitrite ions, nitrogen monoxide or a substance containing NO

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5605617A (en) * 1993-03-29 1997-02-25 Commissariat A L'energie Atomique Conductive polymer film doped by mixed heteropolyanions usable for the detection of nitrite ions, nitrogen monoxide or a substance containing NO

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BENDIKOV, T. ET AL.: "Development and Environmental Application of a Nitrate Selective Microsensor Based on Doped Polypyrrole Films", SENSORS AND ACTUATORS B, vol. 106, 21 September 2004 (2004-09-21), pages 512 - 517 *
BIDAN, G. ET AL.: "Electrode modified by sulfonated calixarenes immobilized into a polypyrrole film: A step towards new ion-sensitive layers", SYNTHETIC METALS, vol. 84, January 1997 (1997-01-01), pages 255 - 256 *
ZINE, N. ET AL.: "All-solid-state hydrogen sensing microelectrodes based on novel PPy[3,3'-Co(1,2-CZB9N'')z] as a solid internai contact", MATERIALS SCIENCE AND ENGINEERING: C, vol. 26, 11 January 2006 (2006-01-11), pages 399 - 404 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9763605B2 (en) 2013-11-27 2017-09-19 Verily Life Sciences Llc Adjustment of sensor sensitivity by controlling copolymer film thickness through a controlled drying step
CN111307911A (zh) * 2018-12-11 2020-06-19 有研工程技术研究院有限公司 一种pH传感器及其制备方法
CN111307911B (zh) * 2018-12-11 2024-01-09 有研工程技术研究院有限公司 一种pH传感器及其制备方法
CN110243899A (zh) * 2019-07-15 2019-09-17 辽宁大学 一种pH敏感石墨烯纳米复合材料及其制备方法和应用
CN113063995A (zh) * 2021-03-16 2021-07-02 中国海洋大学 一种碳基导电聚合物膜水下电场传感器
CN113063995B (zh) * 2021-03-16 2022-12-16 中国海洋大学 一种碳基导电聚合物膜水下电场传感器
CN113500189A (zh) * 2021-08-10 2021-10-15 复旦大学 一种锌微球-聚吡咯可降解复合材料及其界面超组装制备方法

Similar Documents

Publication Publication Date Title
Tajik et al. Recent developments in conducting polymers: Applications for electrochemistry
Yao et al. Electrochemical recognition and trace-level detection of bactericide carbendazim using carboxylic group functionalized poly (3, 4-ethylenedioxythiophene) mimic electrode
Bobacka Conducting polymer‐based solid‐state ion‐selective electrodes
US20110253546A1 (en) Polymer/nanoparticle composites, film and molecular detection device
Bagheri et al. Fabrication of a novel electrochemical sensing platform based on a core–shell nano-structured/molecularly imprinted polymer for sensitive and selective determination of ephedrine
Atta et al. Voltammetric behavior and determination of isoniazid using PEDOT electrode in presence of surface active agents
Wagner et al. Durable PEDOT: PSS films obtained from modified water-based inks for electrochemical sensors
US11525800B2 (en) Biosensor for measuring an analyte concentration
Zuliani et al. A liquid-junction-free reference electrode based on a PEDOT solid-contact and ionogel capping membrane
JP2022132370A (ja) 固体電極及びセンサ
WO2012064179A1 (fr) Capteur de ph
KR20190083120A (ko) 종이 기반의 플렉서블 이온 센서 및 이의 제조방법
WO2012067490A1 (fr) Électrode sélective d'ions
US5869007A (en) Conducting polymer based acid/base sensors
Zine et al. Hydrogen-selective microelectrodes based on silicon needles
Lindfors et al. Study on soluble polypyrrole as a component in all-solid-state ion-sensors
WO2012074368A1 (fr) Capteur de phosphates
WO2013019101A1 (fr) Électrode composite avec polyaniline polymérisée in situ et son procédé de préparation
Pigani et al. PEDOT‐Modified Microelectrodes. Preparation, Characterisation and Analytical Performances
US20170082576A1 (en) An Improved Next Generation Off-Laboratory Polymer Chip Electrode
Yoshida et al. Conducting polymer-coated electrode as a reference/counter electrode in an organic phase and its application to a two-electrode type thin-layer cell for voltammetry at the liquid| liquid interface
Chen et al. Preparation of polyaniline-modified electrodes containing sulfonated polyelectrolytes using layer-by-layer techniques
Yamada et al. All‐solid‐state Fluoride Ion‐selective Electrode using LaF3 Single Crystal with Poly (3, 4‐ethylenedioxythiophene) as Solid Contact Layer
Faridbod et al. Conducting polymer all solid state potentiometric sensor for the tramadol assay
Shahrokhian et al. Electrochemical synthesis of polypyrrole in the presence of congo red; application to selective voltammetric determination of dopamine in the presence of ascorbic acid

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11840230

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11840230

Country of ref document: EP

Kind code of ref document: A1