WO2015040639A1 - Gold coated natural fibre as electrode materials and process for preparation thereof - Google Patents

Gold coated natural fibre as electrode materials and process for preparation thereof Download PDF

Info

Publication number
WO2015040639A1
WO2015040639A1 PCT/IN2014/000613 IN2014000613W WO2015040639A1 WO 2015040639 A1 WO2015040639 A1 WO 2015040639A1 IN 2014000613 W IN2014000613 W IN 2014000613W WO 2015040639 A1 WO2015040639 A1 WO 2015040639A1
Authority
WO
WIPO (PCT)
Prior art keywords
fibre
fibres
gold
natural
gold coated
Prior art date
Application number
PCT/IN2014/000613
Other languages
French (fr)
Other versions
WO2015040639A8 (en
Inventor
Pushipito Kumar Ghosh
Divesh Narayan Srivastava
Dibyendu MONDAL
Mosarrat Perween
Original Assignee
Council Of Scientific And Industrial Research
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 Council Of Scientific And Industrial Research filed Critical Council Of Scientific And Industrial Research
Priority to EP14805680.7A priority Critical patent/EP3047045A1/en
Priority to US15/023,027 priority patent/US20160231269A1/en
Priority to JP2016515535A priority patent/JP2016536569A/en
Publication of WO2015040639A1 publication Critical patent/WO2015040639A1/en
Publication of WO2015040639A8 publication Critical patent/WO2015040639A8/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • 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
    • G01N27/307—Disposable laminated or multilayered electrodes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres

Definitions

  • the present invention relates to gold coated natural fibre as electrode materials comprising natural fibres and gold.
  • the present invention relates to utilisation of cost effective, flexible, mechanically strong and wire shaped coir fibre, jute fibre, banana fibre, sisal fibre, and human hair for electrode preparation. More particularly the natural fibre electrode materials were obtained through sputter coating of thin layered gold on the surface of different natural fibres.
  • the invention relates to use of gold coated natural fibre electrodes as (i) conducting wire, (ii)working electrode materials for the study of cyclic volatammogram of different redox couple in both aqueous and non aqueous media and also in presence of acidic electrolyte, (iii) electrode for arnperometric sensing of hydrogen peroxide, and(iv) anodic stripping voltammetry for detection and quantification of toxic heavy metal ions.
  • the liquid metal Hg, several such as Pt and Au, and other conducting
  • substrates such as graphite are well known electrode materials.
  • Semiconducting materials are also well studied as electrodes in photo-electrochemical processes. Electrochemical processes are conducted on bare electrode surfaces or after various types of modifications such as direct chemical functionalization or through coating of conducting polymers, clays, zeolites, silica, and graphene. Conducting coatings over non conducting substrates are also reported, for example, indium-tin oxide coating on glass that serves as an optically transparent electrode.
  • carbon electrodes such as graphite and carbon paste are well known, such carbon is derived either from a mineral resource or petroleum coke. With the growing interest in the value addition of discarded bioresources, tailor-made electrode materials fabricated from biomaterials will rise in demand.
  • Weavable fibers have been converted into electro active textiles used in super capacitors. Twisting configurations of working and counter electrodes in dye-sensitized-solar-cells have also been studied. Reports on the use of bioresources as electrode material are scant.
  • JP 2004277847A dated 07.10.2004 by Hiramatsu et al., wherein metal-coated coconut fibres and their manufacture by electroplating are disclosed.
  • KR 2004034631 A dated 28.4.2004 by Lee et al., wherein electrode for electric double layer capacitor and method for manufacturing the same is disclosed.
  • JP 63091953 A dated 22.04.1988 by Fuji et al. wherein electrodes and their preparations are disclosed.
  • Composites of woven or nonwoven cloth of conductive fibres mixed with synthetic or natural or regenerated fibres and a polymer of an aromatic compound is used for electrodes.
  • the conductive fibres are obtained by electro less or electroplating of metals on surfaces of synthetic fibres or their mixtures with natural fibres and the electrodes are formed on the fabric by sewing metal thin wires thereon.
  • the main object of the present invention is to provide gold coated natural fibre as electrode materials.
  • Another objective of the present invention is to provide a process for the preparation of sustainable and biodegradable electrode materials thorough simple way from naturally occurring wire shaped fibrous and flexible materials which can be used as alternatives to conventional and synthetic electrode materials.
  • Yet another objective of the present invention is to use mechanically strong coir fibre, jute fibre, sisal fibre, banana fibre, and human hair as non conducting substrate for electrode fabrication.
  • Yet another objective of the present invention is to use gold as noble metal for coating purpose on the surface of natural fibres.
  • Yet another objective of the present invention is to use simple sputter coating technique for gold coating on the surface of the natural fibres.
  • Yet another objective of the present invention is to prove the suitability of the natural fibers electrodes toward detection and quantification of toxic heavy metal ions present in aqueous solution through anodic stripping voltammetry.
  • Yet another objective of the present invention is to check the suitability of these fibers electrodes for ampefometric sensing using hydrogen peroxide as an example.
  • present invention provides gold coated natural fibre electrode materials comprising 5-7% (w/w) of gold and 95-97% (w/w) of natural fibre wherein the natural fibres comprise coir fibre, jute fibre, banana fibre, sisal fibre and human hair.
  • the thickness of the natural fibre is in the range of 2-200 ⁇ .
  • the thickness of the gold on the fibre is in the range of 80- 200 nm.
  • the electrical resistivity of the natural fibre electrodes is in the range of 2x10 "5 - 4x10 "4 ohm cm at 20-30°C.
  • the Young's Modulus of gold coated natural fibre electrodes is in the range of 2 - 30 GPa and % strain at break point in the range of 1-40.
  • thermal stability of the gold coated natural fibre electrodes is in the range of 190-250°C.
  • said electrode materials are useful as working electrode in electrochemical applications including cyclic voltammetry in aqueous and non-aqueous media, anodic stripping voltammetry for detection of lead [Pb(II)], arsenic [As(III)] and mercury [Hg(II)] with detection limit of 69 ppb, 12 ppb and 40 ppb, respectively, and amperometric detection of H2O2.
  • said fibre can be further coated with conducting polymer or subjected to other forms of modification to expand their utility.
  • the present invention can also be readily obtained as aligned fibres such as in the form of a naturally aligned bundle of jute fibre or human hair.
  • the gold coated fibre can be calcined to recover and recycle the gold.
  • present invention provides a process for the preparation of electrically conducting natural fibres comprising the steps of: i. picking individual fibres from sources such as mature coconut, banana stem, jute bark, sisal leaves and head full of hair; ii. washing and drying the fibres if required; iii. alternatively, collecting a bundle of naturally aligned fibres which are fastened at one end through use of a rubber band or clip or glue to retain the alignment; iv. placing the fibres in a conventional sputter coater and carrying out gold coating at 7-8 Pa pressure, 3-4 mA applied plasma current and 20-30 °C temperature over 30-90 minutes to obtain fibres having thickness in the range of 50-200 nm; v. preparing ohmic contact for their fimctioning as working electrode.
  • Figure 1 represents EDX of gold coated coir fibre electrode as obtained in example 1.
  • Figure 3 represents Chronoamperometric response recorded at -0.6 V vs. Ag/AgCl potential for successive addition of 100 of 0.05 M H 2 0 2 to an initial concentration of 100 ⁇ H 2 0 2 .
  • Note calibration curve of limiting current vs. concentration of H 2 0 2 ]. The details are given in example 5.
  • Figure 4 represents anodic stripping voltammogram (ASV) traces for As (III) along with the calibration plot at different concentration of Pb (II) as described in example 6.
  • ASV voltammogram
  • the invention relates to a cost effective and disposable electrode materials fabricated from natural fibres namely, coir fibres, jute fibres, banana fibres, sisal fibres and human hair through sputter coating of gold.
  • natural fibres derived from different bio-resources comprise several useful properties e.g. wire like appearance, flexibility, high mechanical strength, and rough surface.
  • the invention recognised ease of sputter coating technique and was adopted accordingly.
  • Gold was chosen as coating metal recognizing its noble nature and simplicity towards sputter coating. By suitably tuning the gold sputter coating time natural fibres based composites electrode was fabricated which exhibit lower electrical resistivity.
  • composites fibre electrodes By utilizing the composites fibre electrodes in turn, commonly used electrochemical process such as cyclic voltammetry and electrochemical polymerization was tested.
  • the composites fibre electrodes were evaluated in both aqueous and non aqueous solvent. Amperometric sensing of H 2 0 2 and toxic metal ions detection by anodic stripping voltammetry using composites fibre as working electrodes was also demonstrated.
  • the term pristine is used for raw material as obtained.
  • novel inventive steps related to the present invention are as follows: 1. Recognising that low cost, flexible, high mechanical strength, wire shaped natural fibres are an ideal sustainable resource for fabrication of electrically conducting wires and electrodes.
  • fibres are, in many cases, naturally aligned, such as a headful of straight hair, and can be utilized , for naturally aligned mat electrodes.
  • Recognising mat gold can be easily sputter coated on the surface of the natural fibres to create such conducting wires for their functioning as gold electrodes particularly in sensing and detection applications where typically low current densities are encountered.
  • gold electrodes have many useful applications as electrodes by virtue of its inert nature.
  • Jute and sisal fibres (Prerna Stores, Waghawadi Road, Bhavnagar, kann-364002, India) with thickness of 2-10 ⁇ and 40-80 ⁇ respectively, used in the present invention had Young's modulus 25-26 GPa and 20-25 GPa respectively and strain 1-3 % and 8-12 % respectively.
  • the human hairs used in the present invention had thickness 30-50 ⁇ and Young's modulus 2-3 GPa, strain 35-40 %, This example teaches the extraction/source of different natural fibres and their mechanical properties which were used in the present invention.
  • Tensile strength testing was carried out using a universal testing machine (Z wick Roell, type X force P, S/N 756324).
  • Young's modulus (Y) was determined from the regression slope in the elastic region of the stress-strain curve.
  • Au coating of coir fiber was performed using Polaron SC7620 mini-sputter at 8 Pascal pressure.
  • the contacts on the natural fibre electrodes for measurement of I— V characteristics were made using conducting silver paste and copper wire.
  • the copper wire was connected to the source meter unit (SMU) with a crocodile clip.
  • the bias current of ⁇ 1.0 mA was applied, and corresponding voltage was measured.
  • the sweep was generated by the instrument, and 32 measured data points were averaged automatically.
  • the electrical resistances of the natural fibre electrodes were calculated from the slope of the curve.
  • a three-electrode assembly was used in all measurements in which Au-coated coir fiber or Au wire (in control experiment) was used as working electrodes, while platinum foil and Ag/AgCl (sat KC1) were used as auxiliary and reference electrodes, respectively.
  • the contact in the working electrode was made through a spring-loaded clip, which was suitably modified.
  • This example teaches that Young's modulus and strain at breaking point of the natural fibres were in the range of 2-30 GPa and 1-40 %. The example further teaches that maximum strain at breaking point was 35-40 % in case of human hair. This example also teaches amount of gold coated on natural fibres was 5-7 % (w/w) and specific resistivity was in the range of 4c 4 to 2 ⁇ "5 ⁇ cm. Further this example teaches that lowest resistivity was obtained with 2B and 4B respectively. Thickness of gold coating for all samples were in the range of 80-200 nm.
  • Cyclic voltammogram of 0.5 M sulphuric acid was recorded in a 10 mL open cell where gold coated human hair and bare gold act as working electrode while platinum foil and Ag/AgCl (sat KC1) were employed as counter and reference electrode respectively. Scan rate 50 mV/s and potential range -0.2V to 1.6 V was chosen for this experiment.
  • the cyclic voltammogram is provided in Figure 2.
  • This example teaches the stability and cleanness of gold coated natural ⁇ bers in acid media and the similarities of CVs with that of pure gold.
  • the gold coated human hair had clean surface and stable in acidic media.
  • Cyclic voltammetry (CV) of ferrocyanide/ferricyanide redox couple were recorded at 100 mV/s scan rate in a solution having 10 mM potassium ferrocyanide in 0.1 M KC1 using gold coated coir fibre, sisal fibre, jute fibre, banana fibre and human hair as working . electrode. Comparison was also made with a conventional gold wire electrode. The data on peak to peak separation are provided in Table 2. Cyclic voltammetry study in acetonitrile medium was carried out using Au coated natural fibres as working electrode. - CVs were recorded under N 2 atmosphere in an airtight cell.
  • Anilinium sulfate monomer was prepared by dissolving 0.1M aniline in 0.5 M H2SO4 followed by sonication for 6 min. Electro-polymerization was carried out in an open glass cell using 10 mL of freshly prepared monomer. A total of 5-35 potentiodynamic cycles were run in potential window of -0.2 to 0.8 V vs Ag/AgCl. All the natural fibre electrodes could be coated in this manner.
  • Example 5 This example teaches that the surface of the natural fibre electrode can be further modified through electro polymerisation.
  • Hydrogen peroxide was detected using Au coated coir fibre electrode. Amperometric measurements were done in open glass cell containing 10 mL H 2 0 2 (100 ⁇ ) in 0.1 M phosphate buffer (pH 5.2) under continuous stirring. The indicator electrode (coir electrode) was potentiostated at -0.6 V vs. Ag/AgCl. An aliquot of 100 ⁇ - of 0.05 M H 2 0 2 [prepared in 0.1 M phosphate buffer (pH 5.2)] was added successively and the lirniting current was measured after 2 minutes, although the response was instantaneous. The data on H 2 0 2 sensing is given Figure 3.
  • Anodic stripping voltammetric (AS V) detection of heavy metal ions [Pb (II), Hg (II), and As (III)] was attempted on Au coated human hair used as working electrode.
  • Pt foil and Ag/AgCl (saturated KC1) were used as counter and reference electrodes, respectively.
  • 0.1 M acetate buffer of pH 4.0 was used as electrolyte.
  • ASV of Pb (II) a stock solution of 25 ppm (concentration of stock solution was cross checked by ICP analysis) was prepared from 1000 ppm solution of PbCl 2 . Initially, a blank experiment (without any analyte) was run to check the background current.
  • This example teaches use of human hair electrode for ppb level detection and quantification of toxic heavy metals and As(III) in water by ASV.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Electrochemistry (AREA)
  • Textile Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Physical Vapour Deposition (AREA)
  • Non-Insulated Conductors (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Inorganic Fibers (AREA)

Abstract

The present invention relates to gold wires and electrodes fashioned from natural fibres. In particular, fine natural fibres such as coir fibre, jute fibre, sisal fibre, banana fibre, and human hair, which are mechanically strong and flexible, were used as templates over which an 80- 200 nm layer of gold was coated by sputter coating. The composite materials were shown to have low electrical resistivity and functioned normally as electrodes in conventional electrochemical applications such as cyclic voltammetry and anodic stripping voltammetry. Although the present invention focused on the use of single fibres and gold coating exclusively, bundles of naturally aligned fibres and coatings of metals other than gold are logical extensions of the invention.

Description

GOLD COATED NATURAL FIBRE AS ELECTRODE MATERIALS AND
PROCESS FOR PREPARATION THEREOF
FIELD OF THE INVENTION
The present invention relates to gold coated natural fibre as electrode materials comprising natural fibres and gold. Particularly, the present invention relates to utilisation of cost effective, flexible, mechanically strong and wire shaped coir fibre, jute fibre, banana fibre, sisal fibre, and human hair for electrode preparation. More particularly the natural fibre electrode materials were obtained through sputter coating of thin layered gold on the surface of different natural fibres. Still more particularly, the invention relates to use of gold coated natural fibre electrodes as (i) conducting wire, (ii)working electrode materials for the study of cyclic volatammogram of different redox couple in both aqueous and non aqueous media and also in presence of acidic electrolyte, (iii) electrode for arnperometric sensing of hydrogen peroxide, and(iv) anodic stripping voltammetry for detection and quantification of toxic heavy metal ions.
BACKGROUND AND PRIOR ART OF THE INVENTION
The liquid metal, Hg, several such as Pt and Au, and other conducting
Figure imgf000002_0001
substrates such as graphite are well known electrode materials. Semiconducting materials are also well studied as electrodes in photo-electrochemical processes. Electrochemical processes are conducted on bare electrode surfaces or after various types of modifications such as direct chemical functionalization or through coating of conducting polymers, clays, zeolites, silica, and graphene. Conducting coatings over non conducting substrates are also reported, for example, indium-tin oxide coating on glass that serves as an optically transparent electrode. Although carbon electrodes such as graphite and carbon paste are well known, such carbon is derived either from a mineral resource or petroleum coke. With the growing interest in the value addition of discarded bioresources, tailor-made electrode materials fabricated from biomaterials will rise in demand. Weavable fibers have been converted into electro active textiles used in super capacitors. Twisting configurations of working and counter electrodes in dye-sensitized-solar-cells have also been studied. Reports on the use of bioresources as electrode material are scant.
Reference may be made to the article by Ghosh et al. in JACS, 1983, 105, 5691-5693, wherein fabrication of clay modified electrode is disclosed. Reference may be made to the article by Yang et al. in Angew. Chem., Int. Ed. 2013, 52, 7545-7548, wherein photovoltaic wire derived from a graphene composite fiber achieving an 8.45% energy conversion efficiency is reported.
Reference may be made to Guiet al. in ACS Nano 2013, 7, 6037-6046, wherein natural cellulose fiber as substrate for super capacitor is disclosed.
Reference may be made to Chen et al. in Chem. Soc. Rev. 2013, 42, 5031-5041, wherein novel solar cells in a wire format is reviewed.
Reference may be made to the article by Kozan et al. in Biosensors & Bioelectronics, 2010, 25, 1143-1148, wherein amperometric detection of benzoyl peroxide in pharmaceutical preparations using carbon paste electrodes with peroxidases naturally immobilized on coconut fibres is disclosed.
Reference may be made to the article by Kozan et al. In Analytica Chimica Acta, 2007, 591, 200-207, wherein biosensing hydrogen peroxide utilizing carbon paste electrodes containing peroxidases naturally immobilized on coconut (Cocus nucifera L.) fibres is disclosed.
Reference may be made to JP 2004277847A dated 07.10.2004 by Hiramatsu et al., wherein metal-coated coconut fibres and their manufacture by electroplating are disclosed. Reference may be made to KR 2004034631 A dated 28.4.2004 by Lee et al., wherein electrode for electric double layer capacitor and method for manufacturing the same is disclosed.
Reference may be made to JP 63091953 A dated 22.04.1988 by Fuji et al., wherein electrodes and their preparations are disclosed. Composites of woven or nonwoven cloth of conductive fibres mixed with synthetic or natural or regenerated fibres and a polymer of an aromatic compound is used for electrodes. Reference may be made to JP 2002237374 A dated 23.08.2002 by lwakoshi et al., wherein Woven, knitted, or nonwoven fabric made of conductive fibres and equipped with electrodes at certain points are claimed. The conductive fibres are obtained by electro less or electroplating of metals on surfaces of synthetic fibres or their mixtures with natural fibres and the electrodes are formed on the fabric by sewing metal thin wires thereon.
Reference may be made to an article by Bruno et al.in Chemical Communications, 2005, 47, 5896-5898, wherein porous carbon-carbon composite replicated from a natural fibre is disclosed.
Reference may be made to a Patent US 005298048A wherein heat treatable sputter coated glass system is disclosed.
Reference may be made to an article by Bismark et al. in Green Chemistry, 2001, 3, 100-107, wherein Surface characterization of natural fibers; surface properties and the water up-take behavior of modified sisal and coir fibers are disclosed. Reference may be made to an article by Swift et al. in SCANNING VOL. 22, 310-
318 (2000), wherein surface morphology of human hair was investigated by atomic force microscopy (AFM).
Reference may be made to a review article in Advances in Polymer Technology, Vol. 18, No. 4, 351-363 (1999), wherein natural fiber based polymer composites have been documented.
Reference may be made to the ongoing project at "Central Coir Research Institute" Kottayan, India entitled "Design, Development and Analysis of Thin Coated Coir Fiber for Electronic and Other Industrial Applications", wherein the coir fibers were cut in to small tiny pieces and were heated up to a temperature of 1300-1500°C for two hours. It was then powdered and pelletized and coated with silver to use in electronic applications. [http://www.ccriindia.org/thin_film.html; as on 10 September 2014] . Reference may be made to an article in Materials Research 2013, 16(4), 903-923, wherein the authors have coated the gold coir fiber for taking SEM images as a protocol of SEM imaging. The coating is too thin and cannot be used in electrode applications. Reference may be made to an article in Electrochemistry Communications 11
(2009) 764-767, wherein the authors fabricated the gold micro-electrode through chemical liquid deposition method in multiple steps. The conducting surface was achieved after 10- 20 cycles of consecutive deposition taking about 2 days. OBJECTS OF THE INVENTION
The main object of the present invention is to provide gold coated natural fibre as electrode materials.
Another objective of the present invention is to provide a process for the preparation of sustainable and biodegradable electrode materials thorough simple way from naturally occurring wire shaped fibrous and flexible materials which can be used as alternatives to conventional and synthetic electrode materials.
Yet another objective of the present invention is to use mechanically strong coir fibre, jute fibre, sisal fibre, banana fibre, and human hair as non conducting substrate for electrode fabrication.
Yet another objective of the present invention is to use gold as noble metal for coating purpose on the surface of natural fibres.
Yet another objective of the present invention is to use simple sputter coating technique for gold coating on the surface of the natural fibres.
Yet another objective of the present invention is to fine tune the coating time to raise conductivity of the naturals fibres electrode and to value add the fibre for different electro chemical processes. Yet another objective of the present invention is to check the suitability of the natural fiber electrode materials as working electrode for the study of cyclic voltammetry in both aqueous and non-aqueous media. Yet another objective of the present invention is to verify the suitability of the natural fiber electrode materials for further surface modification through electro polymerisation process taking aniline as an example.
Yet another objective of the present invention is to prove the suitability of the natural fibers electrodes toward detection and quantification of toxic heavy metal ions present in aqueous solution through anodic stripping voltammetry.
Yet another objective of the present invention is to check the suitability of these fibers electrodes for ampefometric sensing using hydrogen peroxide as an example.
SUMMARY OF THE INVENTION
Accordingly, present invention provides gold coated natural fibre electrode materials comprising 5-7% (w/w) of gold and 95-97% (w/w) of natural fibre wherein the natural fibres comprise coir fibre, jute fibre, banana fibre, sisal fibre and human hair.
In an embodiment of the present invention, the thickness of the natural fibre is in the range of 2-200 μτη.
In another embodiment of the present invention, the thickness of the gold on the fibre is in the range of 80- 200 nm.
In yet another embodiment of the present invention, the electrical resistivity of the natural fibre electrodes is in the range of 2x10"5 - 4x10"4 ohm cm at 20-30°C. In yet another embodiment of the present invention, the Young's Modulus of gold coated natural fibre electrodes is in the range of 2 - 30 GPa and % strain at break point in the range of 1-40. In yet another embodiment of the present invention, thermal stability of the gold coated natural fibre electrodes is in the range of 190-250°C.
In yet another embodiment of the present invention, said electrode materials are useful as working electrode in electrochemical applications including cyclic voltammetry in aqueous and non-aqueous media, anodic stripping voltammetry for detection of lead [Pb(II)], arsenic [As(III)] and mercury [Hg(II)] with detection limit of 69 ppb, 12 ppb and 40 ppb, respectively, and amperometric detection of H2O2. In yet another embodiment of the present invention, said fibre can be further coated with conducting polymer or subjected to other forms of modification to expand their utility.
In yet another embodiment of the present invention, it can be employed in microelectronics by virtue of their electrical conductivity, flexibility, mechanical stability and micron level thickness.
In yet another embodiment of the present invention, it can also be readily obtained as aligned fibres such as in the form of a naturally aligned bundle of jute fibre or human hair. In yet another embodiment of the present invention, the gold coated fibre can be calcined to recover and recycle the gold.
In yet another embodiment, present invention provides a process for the preparation of electrically conducting natural fibres comprising the steps of: i. picking individual fibres from sources such as mature coconut, banana stem, jute bark, sisal leaves and head full of hair; ii. washing and drying the fibres if required; iii. alternatively, collecting a bundle of naturally aligned fibres which are fastened at one end through use of a rubber band or clip or glue to retain the alignment; iv. placing the fibres in a conventional sputter coater and carrying out gold coating at 7-8 Pa pressure, 3-4 mA applied plasma current and 20-30 °C temperature over 30-90 minutes to obtain fibres having thickness in the range of 50-200 nm; v. preparing ohmic contact for their fimctioning as working electrode.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 represents EDX of gold coated coir fibre electrode as obtained in example 1.
Figure 2 represents cyclic voltammogram of 0.5 M sulphuric acid on Au coated human hair electrode (red), and bare gold electrode (black) at scan rate = 50 mV/s.
Figure 3 represents Chronoamperometric response recorded at -0.6 V vs. Ag/AgCl potential for successive addition of 100 of 0.05 M H202 to an initial concentration of 100 μΜ H202. [Inset: calibration curve of limiting current vs. concentration of H202]. The details are given in example 5.
Figure 4 represents anodic stripping voltammogram (ASV) traces for As (III) along with the calibration plot at different concentration of Pb (II) as described in example 6.
DETAILED DESCRIPTION OF THE INVENTION
The invention relates to a cost effective and disposable electrode materials fabricated from natural fibres namely, coir fibres, jute fibres, banana fibres, sisal fibres and human hair through sputter coating of gold. The invention recognised that the natural fibres derived from different bio-resources comprise several useful properties e.g. wire like appearance, flexibility, high mechanical strength, and rough surface. In targeting a suitable method, the invention recognised ease of sputter coating technique and was adopted accordingly. Gold was chosen as coating metal recognizing its noble nature and simplicity towards sputter coating. By suitably tuning the gold sputter coating time natural fibres based composites electrode was fabricated which exhibit lower electrical resistivity. By utilizing the composites fibre electrodes in turn, commonly used electrochemical process such as cyclic voltammetry and electrochemical polymerization was tested. The composites fibre electrodes were evaluated in both aqueous and non aqueous solvent. Amperometric sensing of H202 and toxic metal ions detection by anodic stripping voltammetry using composites fibre as working electrodes was also demonstrated.
Accordingly, a cost effective and flexible natural fibre based composite electrode materials is disclosed. The preparation of gold coated natural fibre electrodes comprising:
(i) Physically picking individual coir fibre strands from mature coconut; banana fibres from chemically treated banana stem as taught in the prior art; jute fibres from physically treated jute bark; sisal fibres from sisal leaves; and human hair from head full of hair;
(ii) washing and drying the fibres before used whenever required;
(Hi) Alternatively, collecting a bundle of naturally aligned jute fibres or human hair which are clipped or glued to retain the alignment;
(iv) Placing a bundle of natural fibres in a conventional sputter coater and carrying out gold coating.
(v) Removing the gold coated natural fibres from sputter coater chamber and ensuring ohmic contact for their functioning as electrode materials.
(vi) Finally, testing of the composite fibre electrodes for well known electrochemical experiments such cyclic voltammetry, electro-polymerisation of aniline.
(vii) Testing the suitability of the natural fibre electrodes towards amperometric detection of ¾<¾ and detection of toxic heavy metal ions by anodic stripping voltammetry.
The term pristine is used for raw material as obtained.
The novel inventive steps related to the present invention are as follows: 1. Recognising that low cost, flexible, high mechanical strength, wire shaped natural fibres are an ideal sustainable resource for fabrication of electrically conducting wires and electrodes.
2. Recognising that some of the natural fibres such as jute fibre are extremely fine and wires made from these may be quite useful in microelectronics.
3. Recognising further that such fibres are, in many cases, naturally aligned, such as a headful of straight hair, and can be utilized , for naturally aligned mat electrodes.
4. Recognising mat gold can be easily sputter coated on the surface of the natural fibres to create such conducting wires for their functioning as gold electrodes particularly in sensing and detection applications where typically low current densities are encountered.
5. Recognizing that not only is gold easy to coat, gold electrodes have many useful applications as electrodes by virtue of its inert nature.
6. Further recognising that an 80-200 nm gold coating suffices for this purpose, this amounting to 5-7% of the total weight of the composite electrode.
7. Further demonstrating best performance with jute fibre and human hair in so far as electrical resistivity and peak-to-peak separation in cyclic voltammetry are concerned.
8. Further demonstrating the utility of the electrode made from human hair in anodic stripping voltammetry with ppb level detection.
EXAMPLES
Following examples are given by" way of illustration and should not be construed to limit
Figure imgf000010_0001
invention.
Materials and methods Dry coir fibres of uniform diameter (150-200 μιη), having Young's modulus 5-7 GPa and strain 7-11 % was physically picked from fully matured coconut fruit (Prerna Stores, Waghawadi Road, Bhavnagar, Gujarat-364002, India) and selected for the study without any chemical pre-treatment. Banana fibre (Prerna Stores, Waghawadi Road, Bhavnagar, Gujarat- 364002, India) was extracted by known method of chemical pretreatment. Thus obtained banana fibres had thickness 10-30 μπι, Young's modulus 7-10 GPa and strain 2-4 %. Jute and sisal fibres (Prerna Stores, Waghawadi Road, Bhavnagar, Gujarat-364002, India) with thickness of 2-10 μπι and 40-80 μιη respectively, used in the present invention had Young's modulus 25-26 GPa and 20-25 GPa respectively and strain 1-3 % and 8-12 % respectively. The human hairs used in the present invention had thickness 30-50 μπι and Young's modulus 2-3 GPa, strain 35-40 %, This example teaches the extraction/source of different natural fibres and their mechanical properties which were used in the present invention. Tensile strength testing was carried out using a universal testing machine (Z wick Roell, type X force P, S/N 756324). Young's modulus (Y) was determined from the regression slope in the elastic region of the stress-strain curve. Au coating of coir fiber was performed using Polaron SC7620 mini-sputter at 8 Pascal pressure. The thickness of Au coating on the surface of the fibre was determined using the following equation. d = KlVt (1) where d is the coating thickness in angstrom; K is an experimentally determined constant (for Au used with air, K = 0.07 approximately); I is the plasma current in mA (5 mA in present invention), V is the bias voltage in kV (1 kV in present invention), and t is the sputtering time in seconds (3600 s in present invention). Current-voltage (I— V) measurements were performed using a Keithley 2635A source meter unit (SMU). The contacts on the natural fibre electrodes for measurement of I— V characteristics were made using conducting silver paste and copper wire. The copper wire was connected to the source meter unit (SMU) with a crocodile clip. The bias current of ±1.0 mA was applied, and corresponding voltage was measured. The sweep was generated by the instrument, and 32 measured data points were averaged automatically. The averaged arid stored data "were" collected and plotted to obtain the I— V curve. The electrical resistances of the natural fibre electrodes were calculated from the slope of the curve. The specific resistance of the coating was calculated considering it as a sheet and applying the equations: Specific resistance p = R * (W x L)/H; wherein W is the width of the sheet (thickness of the coating), L is length of the sheet (circumference of the coating, i.e., 2πτ), H is height (length of the fiber between two contacts); and R is measured resistance (from slope of I-V curve). Electrochemical experiments were performed using a Princeton applied research potentiostat (PAR-STAT 2273) at room temperature (24±2 °C). A three-electrode assembly was used in all measurements in which Au-coated coir fiber or Au wire (in control experiment) was used as working electrodes, while platinum foil and Ag/AgCl (sat KC1) were used as auxiliary and reference electrodes, respectively. The contact in the working electrode was made through a spring-loaded clip, which was suitably modified. Example 1
For coatings of Au, a bundle of coir fibers (75 to 100) as described in materials and method section were placed into the chamber of a sputter coater (100 mm diameter * 100 mm height). The vapor pressure of gold was maintained uniformly in the chamber which facilitated uniform coating. After 60 min of coating, the fibers were removed from the coater and characterized. The data on physical properties of different fibres are provided in Table 1 and EDX of gold coated coir fibre is given as Figure 1. i
This example teaches that Young's modulus and strain at breaking point of the natural fibres were in the range of 2-30 GPa and 1-40 %. The example further teaches that maximum strain at breaking point was 35-40 % in case of human hair. This example also teaches amount of gold coated on natural fibres was 5-7 % (w/w) and specific resistivity was in the range of 4c 4 to 2ε"5Ω cm. Further this example teaches that lowest resistivity was obtained with 2B and 4B respectively. Thickness of gold coating for all samples were in the range of 80-200 nm.
Table 1 Different physical properties of uncoated and gold coated natural fibre electrode.
Figure imgf000012_0001
Figure imgf000013_0001
ND= Not determined; 1A= uncoated coir fibre; 1B= Au coated coir fibre; 2A= uncoated human hair; 2B= Au coated human hair; 3A= uncoated sisal fibre; 3B= Au coated sisal fibre; 4A= uncoated jute fibre; 4B= Au coated jute fibre; 5A= uncoated banana fibre; and 5B= Au coated banana fibre.
Example 2
Cyclic voltammogram of 0.5 M sulphuric acid was recorded in a 10 mL open cell where gold coated human hair and bare gold act as working electrode while platinum foil and Ag/AgCl (sat KC1) were employed as counter and reference electrode respectively. Scan rate 50 mV/s and potential range -0.2V to 1.6 V was chosen for this experiment. The cyclic voltammogram is provided in Figure 2.
This example teaches the stability and cleanness of gold coated natural ^bers in acid media and the similarities of CVs with that of pure gold. The gold coated human hair had clean surface and stable in acidic media.
Example 3
Cyclic voltammetry (CV) of ferrocyanide/ferricyanide redox couple were recorded at 100 mV/s scan rate in a solution having 10 mM potassium ferrocyanide in 0.1 M KC1 using gold coated coir fibre, sisal fibre, jute fibre, banana fibre and human hair as working . electrode. Comparison was also made with a conventional gold wire electrode. The data on peak to peak separation are provided in Table 2. Cyclic voltammetry study in acetonitrile medium was carried out using Au coated natural fibres as working electrode. - CVs were recorded under N2 atmosphere in an airtight cell. One mM solution of [Ru(bpy)3]Cl2 was prepared in dry acetonitrile in the presence of 0.1 M tetraethylammonium tetrafluoroborate (supporting electrolyte). N2 was purged for 10 min before start of the experiment. CVs were recorded at 350 mV/s scan rate without any agitation. The data on peak to peak separation is given in Table 2. Table 2: Peak to peak separation in aqueous and non aqueous media for different natural fibre electrodes.
Figure imgf000014_0001
1B= Au coated coir fibre; 2B= Au coated human hair; 3B= Au coated sisal fibre; 4B= Au coated jute fibre; and 5B= Au coated banana fibre.
This example teaches that the peak to peak separation in aqueous and nonaqueous media mirrored the trends of specific resistivity as mention in Table 1, the separations being the least for jute fibre and human hair. For comparison, the peak-to-peak separation recorded on conventional gold wire electrode is also shown in the table.
Example 4
An attempt was made to electrochemically coat polyaniline over the surface of the natural fibre electrodes. Anilinium sulfate monomer was prepared by dissolving 0.1M aniline in 0.5 M H2SO4 followed by sonication for 6 min. Electro-polymerization was carried out in an open glass cell using 10 mL of freshly prepared monomer. A total of 5-35 potentiodynamic cycles were run in potential window of -0.2 to 0.8 V vs Ag/AgCl. All the natural fibre electrodes could be coated in this manner.
This example teaches that the surface of the natural fibre electrode can be further modified through electro polymerisation. Example 5
Hydrogen peroxide was detected using Au coated coir fibre electrode. Amperometric measurements were done in open glass cell containing 10 mL H202 (100 μΜ) in 0.1 M phosphate buffer (pH 5.2) under continuous stirring. The indicator electrode (coir electrode) was potentiostated at -0.6 V vs. Ag/AgCl. An aliquot of 100 μί- of 0.05 M H202 [prepared in 0.1 M phosphate buffer (pH 5.2)] was added successively and the lirniting current was measured after 2 minutes, although the response was instantaneous. The data on H202 sensing is given Figure 3.
This example teaches amperometric detection of hydrogen peroxide can done using coir fibre electrode. The responses were found instantaneous indicating efficient electron transfer through the coir electrode. The detection limit was found to be όχΐθ"4 M. Example 6
Anodic stripping voltammetric (AS V) detection of heavy metal ions [Pb (II), Hg (II), and As (III)] was attempted on Au coated human hair used as working electrode. Pt foil and Ag/AgCl (saturated KC1) were used as counter and reference electrodes, respectively. 0.1 M acetate buffer of pH 4.0 was used as electrolyte. For ASV of Pb (II), a stock solution of 25 ppm (concentration of stock solution was cross checked by ICP analysis) was prepared from 1000 ppm solution of PbCl2. Initially, a blank experiment (without any analyte) was run to check the background current. Thereafter certain volume (10-40 μΐ,) of Pb (II) stock solution f was added successively in a cell containing 10 mL acetate buffer. Electrode position was carried out by applying -0.8 V for 10 minutes under stirring condition. Subsequently, a square wave voltammetry waveform was applied in the range of -0.3 to 0.3V to obtain a stripping voltammogram maintaining25 mV pulse width for lOmillisecond and step height 2mV. The electrode was washed after each experiment by applying 0.8V potential in blank electrolyte for 10 minutes. To insure complete washing the process was repeated several time and checked for any oxidation peak if there. Peak current values were corrected from background current associated with blank scan. The corrected values of peak current and concentration were used to draw calibration plot. For ASV of Hg (II), 25 ppm stock solution of Hg (II) was prepared from 1000 ppm solution of HgCl2. The scanning potential range was -0.6 to 0.7V. The other experimental conditions were same as mentioned above. For ASV of As (III), 25 ppm stock solution of As (III) was prepared from 1000 ppm solution of AS2O3. The scanning potential range was -0.5 to 1.0V. The other experimental conditions were same as mentioned above. Figure 4 shows the ASV traces for As(III) along with the calibration plot. Table 3 provides data on the detection limits of Pb(II), Hg(II) and As(III). Table 3:Data on lower detection limit of Pb (II), Hg (II), and As (III) as obtained by anodic stripping voltammetry on gold coated human hair as working electrode.
Figure imgf000016_0001
This example teaches use of human hair electrode for ppb level detection and quantification of toxic heavy metals and As(III) in water by ASV.
ADVANTAGES OF THE INVENTION
The advantages of the present invention are-
(i) Use of inexpensive natural fibres bestowed with excellent properties such as high strength, flexibility and natural alignment of bundles of fibres in several cases as sustainable resources for fabrication of electrically conducting wires and electrodes.
(ii) Ease of preparation of such electrically conducting natural wires and electrodes through sputter coating of gold.
(iii) A true composite electrode wherein useful properties such as flexibility, mechanical strength, fineness are drawn from the inexpensive natural fibres whereas electrical conductivity is drawn from precious gold, and as a result minimizing the requirement of gold to only 5-7% of total weight as compared to a conventional gold electrode.
(iv) Recognising that although gold coated natural fibre electrodes would have lower current carrying capacity than bulk gold wire, such electrodes adequately serve the purpose in electrochemical sensing applications where low current density is required.
(v) Gold can be recycled and reused after burning the natural fibre.

Claims

Gold coated natural fibre electrode materials comprising 5-7% (w/w) of gold and 95 - 97%(w/w) of natural fibre wherein the natural fibres comprise coir fibre, jute fibre, banana fibre, sisal fibre and human hair.
The gold coated natural fibre as claimed in Claims 1, wherein the thickness of the natural fibre is in the range of 2-200 μπι.
The gold coated natural fibre as claimed in claim 1, wherein the thickness of the gold on the fibre is in the range of 80- 200 nm.
The gold coated natural fibre as claimed in claim 1, wherein the electrical resistivity of the natural fibre electrodes is in the range of 2x10"5 - 4x10"4 ohm cm at 20-30°C.
The gold coated natural fibre as claimed in claim 1, wherein the Young's Modulus of gold coated natural fibre electrodes is in the range of 2 - 30 GPa and % strain at break point in the range of 1-40.
The gold coated natural fibre as claimed in claim 1, wherein thermal stability of the gold coated natural fibre electrodes is in the range of 190-250°C.
The gold coated natural fibre as claimed in claim 1, wherein said electrode materials are useful as working electrode in electrochemical applications including cyclic voltammetry in aqueous and non-aqueous media, anodic stripping voltammetry for detection of lead [Pb(II)], arsenic [As(III)] and mercury [Hg(II)] with detection limit of 69 ppb, 12 ppb and 40 ppb, respectively, and amperometric detection of H202.
The gold coated natural fibre as claimed in claim 1, wherein said fibre can be further coated with conducting polymer or subjected to other forms of modification to expand their utility.
Electrically conducting natural fibres as claimed in claims 1-8, wherein it can be employed in microelectronics by virtue of their electrical conductivity, flexibility, mechanical stability and micron level thickness. Electrically conducting natural fibres as claimed in claims 1-9, wherein it can also be readily obtained as aligned fibres such as in the form of a naturally aligned bundle of jute fibre or human hair.
Electrically conducting natural fibres as claimed in claims 1-10, wherein the gold coated fibre can be calcined to recover and recycle the gold.
A process for the preparation of electrically conducting natural fibres comprising the steps of: i. picking individual fibres from sources such as mature coconut, banana stem, jute bark, sisal leaves and head full of hair; ii. washing and drying the fibres if required; iii. alternatively, collecting a bundle of naturally aligned fibres which are fastened at one end through use of a rubber band or clip or glue to retain the alignment; iv. placing the fibres in a conventional sputter coater and carrying out gold coating at 7-8 Pa pressure, 3-4 mA applied plasma current and 20-30 °C temperature over 30-90 minutes to obtain fibres having thickness in the range of 50-200 nm; v. preparing ohmic contact for their functioning as working electrode.
PCT/IN2014/000613 2013-09-19 2014-09-19 Gold coated natural fibre as electrode materials and process for preparation thereof WO2015040639A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP14805680.7A EP3047045A1 (en) 2013-09-19 2014-09-19 Gold coated natural fibre as electrode materials and process for preparation thereof
US15/023,027 US20160231269A1 (en) 2013-09-19 2014-09-19 Gold coated natrual fibre as electrode materials and process for preparation thereof
JP2016515535A JP2016536569A (en) 2013-09-19 2014-09-19 Natural fiber coated with gold as electrode material and process for its preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2755DE2013 2013-09-19
IN2755/DEL/2013 2013-09-19

Publications (2)

Publication Number Publication Date
WO2015040639A1 true WO2015040639A1 (en) 2015-03-26
WO2015040639A8 WO2015040639A8 (en) 2015-06-04

Family

ID=52000908

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2014/000613 WO2015040639A1 (en) 2013-09-19 2014-09-19 Gold coated natural fibre as electrode materials and process for preparation thereof

Country Status (4)

Country Link
US (1) US20160231269A1 (en)
EP (1) EP3047045A1 (en)
JP (1) JP2016536569A (en)
WO (1) WO2015040639A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10191009B2 (en) * 2015-03-05 2019-01-29 University Of Louisville Research Foundation, Inc. Electrochemical determination of heavy metals
CN105466989B (en) * 2015-12-18 2018-06-29 浙江工业大学 The electrochemical detection method of lead in a kind of soy sauce
DE112023001482T5 (en) * 2022-03-22 2025-01-09 Ntt Research, Inc. FLEXIBLE DRY ELECTRODES
CN115985553B (en) * 2023-01-13 2024-09-17 上海怡上电子科技有限公司 Halogen-free silver paste with high bending resistance and preparation method thereof
DE102023104347A1 (en) 2023-02-22 2024-08-22 Schunk Kohlenstofftechnik Gmbh Electrical conductor for an electrosurgical instrument and method for its manufacture, electrosurgical instrument, electrosurgical device and use of a material for producing an electrical conductor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6391953A (en) 1986-10-03 1988-04-22 Mitsubishi Petrochem Co Ltd Electrode and its manufacturing method
US5298048A (en) 1991-12-09 1994-03-29 Guardian Industries Corp. Heat treatable sputter-coated glass systems
JP2002237374A (en) 2001-02-08 2002-08-23 Yukari Iwakoshi Flexible flat heating element
KR20040034631A (en) 2004-03-15 2004-04-28 (주) 스마트씽커즈 Electrode for electric double layer capacitor and method for fabricating the same
JP2004277847A (en) 2003-03-18 2004-10-07 Okayama Prefecture Plating palm fiber and method for producing the plating palm fiber

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6391953A (en) 1986-10-03 1988-04-22 Mitsubishi Petrochem Co Ltd Electrode and its manufacturing method
US5298048A (en) 1991-12-09 1994-03-29 Guardian Industries Corp. Heat treatable sputter-coated glass systems
JP2002237374A (en) 2001-02-08 2002-08-23 Yukari Iwakoshi Flexible flat heating element
JP2004277847A (en) 2003-03-18 2004-10-07 Okayama Prefecture Plating palm fiber and method for producing the plating palm fiber
KR20040034631A (en) 2004-03-15 2004-04-28 (주) 스마트씽커즈 Electrode for electric double layer capacitor and method for fabricating the same

Non-Patent Citations (15)

* Cited by examiner, † Cited by third party
Title
ADVANCES IN POLYMER TECHNOLOGY, vol. 18, no. 4, 1999, pages 351 - 363
BISMARK ET AL., GREEN CHEMISTRY, vol. 3, 2001, pages 100 - 107
BRUNO, CHEMICAL COMMUNICATIONS, vol. 47, 2005, pages 5896 - 5898
CHEN ET AL., CHEM. SOC. REV., vol. 42, 2013, pages 5031 - 5041
ELECTROCHEMISTRY COMMUNICATIONS, vol. 11, 2009, pages 764 - 767
GHOSH ET AL., JACS, vol. 105, 1983, pages 5691 - 5693
GUIET, ACS NANO, vol. 7, 2013, pages 6037 - 6046
KOZAN ET AL., BIOSENSORS & BIOELECTRONICS, vol. 25, 2010, pages 1143 - 1148
KOZAN ET AL., IN ANALYTICA CHIMICA ACTA, vol. 591, 2007, pages 200 - 207
MATERIALS RESEARCH, vol. 16, no. 4, 2013, pages 903 - 923
MONDAL D; PERWEEN M; SRIVASTAVA D N; GHOSH P K: "Unconventional electrode material prepared from coir fiber through sputter coating of gold: A study toward value addition of natural biopolymer", ACS SUSTAINABLE CHEMISTRY AND ENGINEERING, vol. 2, 8 December 2013 (2013-12-08), USA, pages 348 - 352, XP002736496, DOI: 10.1021/sc400389u *
SVOBODA ET AL: "Differential-pulse anodic stripping voltammetry of mercury with gold-film micro-electrodes", ANALYTICA CHIMICA ACTA, ELSEVIER, AMSTERDAM, NL, vol. 166, 1 January 1985 (1985-01-01), pages 297 - 299, XP022091723, ISSN: 0003-2670, DOI: 10.1016/S0003-2670(00)84879-5 *
SWIFT ET AL., SCANNING, vol. 22, 2000, pages 310 - 318
XU J ET AL: "Ultrathin gold film deposited on human hair: Derivation from nanoparticles and applications as microsensors", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 11, no. 4, 1 April 2009 (2009-04-01), pages 764 - 767, XP026075550, ISSN: 1388-2481, [retrieved on 20090131], DOI: 10.1016/J.ELECOM.2009.01.028 *
YANG ET AL., ANGEW. CHEM., INT. ED., vol. 52, 2013, pages 7545 - 7548

Also Published As

Publication number Publication date
US20160231269A1 (en) 2016-08-11
JP2016536569A (en) 2016-11-24
EP3047045A1 (en) 2016-07-27
WO2015040639A8 (en) 2015-06-04

Similar Documents

Publication Publication Date Title
Chen et al. An efficient flexible electrochemical glucose sensor based on carbon nanotubes/carbonized silk fabrics decorated with Pt microspheres
Kakhki A review to recent developments in modification of carbon fiber electrodes
Peng et al. Flexible polypyrrole/copper sulfide/bacterial cellulose nanofibrous composite membranes as supercapacitor electrodes
Molina Graphene-based fabrics and their applications: a review
Li et al. High-performance all-solid-state supercapacitor derived from PPy coated carbonized silk fabric
Chen et al. Synthesis of aligned carbon nanotube composite fibers with high performances by electrochemical deposition
Balasubramanian et al. Electrochemically functionalized carbon nanotubes for device applications
Pasta et al. Aqueous supercapacitors on conductive cotton
Guo et al. Highly sensitive simultaneous electrochemical detection of hydroquinone and catechol with three-dimensional N-doping carbon nanotube film electrode
US20160231269A1 (en) Gold coated natrual fibre as electrode materials and process for preparation thereof
Du et al. One-step electrochemical deposition of Prussian Blue–multiwalled carbon nanotube nanocomposite thin-film: preparation, characterization and evaluation for H 2 O 2 sensing
Ruiyi et al. Histidine-functionalized graphene quantum dot-graphene micro-aerogel based voltammetric sensing of dopamine
Shao et al. Fabrication of polyaniline/graphene/polyester textile electrode materials for flexible supercapacitors with high capacitance and cycling stability
Peng et al. Flexible polypyrrole/cobalt sulfide/bacterial cellulose composite membranes for supercapacitor application
Sapountzi et al. One-step fabrication of electrospun photo-cross-linkable polymer nanofibers incorporating multiwall carbon nanotubes and enzyme for biosensing
Zhang et al. An acetylcholinesterase biosensor with high stability and sensitivity based on silver nanowire–graphene–TiO 2 for the detection of organophosphate pesticides
Li et al. 3D electrochemical sensor based on poly (hydroquinone)/gold nanoparticles/nickel foam for dopamine sensitive detection
Jo et al. Calligraphic ink enabling washable conductive textile electrodes for supercapacitors
Qiu et al. Graphene oxide directed in-situ synthesis of Prussian blue for non-enzymatic sensing of hydrogen peroxide released from macrophages
Sriwichai et al. Fabrication and characterization of electrospun poly (3-aminobenzylamine)/functionalized multi-walled carbon nanotubes composite film for electrochemical glucose biosensor
Fernández et al. Study on the specific capacitance of an activated carbon cloth modified with reduced graphene oxide and polyaniline by cyclic voltammetry
Karuppusamy et al. Highly conductive nano-silver textile for sensing hydrogen peroxide
Mary et al. Supercapacitor and non-enzymatic biosensor application of an Mn 2 O 3/NiCo 2 O 4 composite material
Elrouby Electrochemical applications of carbon nanotube
Yang et al. Ag nanowires functionalized cellulose textiles for supercapacitor and photothermal conversion

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: 14805680

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016515535

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 15023027

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2014805680

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2014805680

Country of ref document: EP