• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Electrode for the detection of metals, simple and that does not require the previous deposition of bismuth on a carbon basis, as well as the manufacturing process of the electrode, which comprises a plastic support sheet, an active part on said sheet, a conductive part arranged on a portion of the active part and extending on the plastic support sheet, an insulating part covering the central area of the plastic support sheet so that a portion of the active part and a portion of the conductive part on the the same opposite to the active part, on the active part carbon nanofibers and bismuth nanoparticles are fixed, and on the active part a plastic mask with a through hole is placed, the sample is deposited in said through hole. The fixation of the nanofibers and nanoparticles is done by filtering. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2612335A1
    申请号:ES201531640
    申请日:2015-11-13
    公开日:2017-05-16
    发明作者:Susana PALMERO DÍAZ；Ana Erica PÁRAMO MARTÍN
    申请人:Universidad de Burgos；
    IPC主号:
    专利说明:

    METAL DETECTION ELECTRODE
    DESCRIPTION
    OBJECT OF THE INVENTION 5

    The present invention relates to an electrode for the detection of metals and its manufacturing process, the electrode comprises a support sheet on which an active part is provided that includes bismuth and carbon, a conductive part and an insulating part, so that prior bismuth deposition on a carbon basis is not required.
    BACKGROUND OF THE INVENTION 15

    For the detection of metals, in recent years bismuth electrodes have been proposed as an alternative to voltammetric scanning stripping due to their low toxicity and wide electrochemical window (I. Švancara et al., Electroanalysis, 2010, 22, 1405–1420). Bismuth film electrodes (BiFEs) are manufactured with a layer of bismuth deposited on a conductive substrate such as graphite, vitrified carbon, carbon nanofibers or 25 carbon paste electrodes (J. Wang, Electroanalysis, 2005, 17, 1341– 1346). These electrodes can replace mercury electrodes in voltammetric scanning (C. Kokkinos et al., Curr. Anal. Chem., 2008, 4, 183-190), shown in US Patent 6,682,647.

    The most widely used method for the preparation of BiFEs is electrochemical deposition (potentiometry, pulse amperometry or
    cyclic voltammetry) on a conductive support (J. Barón-Jaimez et al., J. Phys. Conf. Ser., 2013, 466, 012025), modified carbon paste electrodes, bismuth oxide (R. Metelka et al. Electrochem. Commun. 2002, 4, 193-196) or bismuth nanoparticles. An advantage of these electrodes is the possibility of miniaturization of the electrochemical cell and therefore different models have been developed and described in the literature (V. Dos Santos et al., Talanta, 2014, 126, 82-90). 10

    However, this methodology involves the use of Bi (III) salts that can complicate experimental procedures (C. Kokkinos et al., Electrochim. Acta., 2008, 53, 5294–5299). Cases are known where the introduction of bismuth ions into the solution from the stage of formation of the bismuth film is undesirable, which may cause interference in subsequent measurements in the electrochemical cell in addition to increasing the time of experimentation. because prior to the measure, the said deposition must be carried out.

    One possible solution is to develop a bismuth nanoparticle electrode by coating the conductive carbon layer 25 and the flexible polymer film using screen-printed electrode technology (G.-J. Lee et al., Electrochem. Commun., 2007, 9, 2514–2518) or prepare a modified electrode with bismuth nanoparticles (H. Yang et al., Mater. Res. 30 Bull., 2013, 48, 4718–4722; G. March et al., Biosensors, 2015, 5, 241-275).
    DESCRIPTION OF THE INVENTION
     35
    The present invention is established and characterized in the independent claims, while the dependent claims describe other features thereof.
     5
    The object of the invention is an electrode for the detection of metals, simple and which does not require, for its active part, the previous deposition of bismuth on a carbon base, as well as the method of manufacturing the electrode. The technical problem to be solved is to configure the electrode with its components and establish the manufacturing stages of the electrode to achieve the object mentioned.

    One advantage is that the electrode is low cost 15 because plastic materials are used. Likewise, it can be made of small size, which facilitates its transport and storage, while allowing to control the active surface of the electrode and use small quantities of samples (of the order of microliters). twenty

    Another advantage derived from the materials and the structure specified in the claims is that it has a longer useful life with respect to bismuth electrodes manufactured in situ, thus it can be used in a complete experience including pre-calibrating, since the surface of the The electrode can be regenerated with a simple electrochemical cleaning and can be used a certain number of times.
     30 DESCRIPTION OF THE FIGURES

    The present specification is complemented by a set of figures, illustrative of the preferred example and never limiting of the invention. 35

    Figure 1 represents a perspective view of the electrode support sheet, the active part and the conductive part.
     5
    Figure 2 represents the electrode of Figure 1 to which the insulating part has been added.

    Figure 3 represents the electrode of Figure 2 to which the mask has been added. 10

    Figure 4 represents a perspective view of the active part with carbon nanofibers and bismuth nanoparticles.
     fifteen
    Figure 5 represents a perspective view of an electrode with a sample and connections for measuring it.
    DETAILED EXHIBITION OF THE INVENTION 20

    An embodiment of the invention is shown below with support in the figures.

    In Figures 3 and 5 an electrode for metal detection in a sample (6) comprising:
    -a plastic support sheet (1), preferably of polyethylene terephthalate (PET);
    - an active part (2) disposed on the plastic support sheet (1) and comprising a plastic base 30 (2.1), shown in Figure 4, this preferably made of polytetrafluoroethylene (PTFE);
    - a conductive part (3) disposed on a portion of the active part (2) and extending on the plastic support sheet (1), preferably comprises
    silver (Ag);
    - an insulating part (4) covering the central area of the plastic support sheet (1) so that a portion of the active part (2) and a portion of the conductive part (3) on the side of the sheet is free (1) opposite the active part (2), preferably said insulating part (4) comprises an epoxy resin with mineral filler.

    As shown in Figure 4, carbon nanofibers (2.2) and bismuth nanoparticles (2.3) are fixed on the plastic base (2.1) of the active part (2), and on the active part (2), shown in Figure 3, a plastic mask (5) is provided, preferably comprising polytetrafluoroethylene (PTFE), 15 with a through hole (5.1) so that the sample (6) is deposited in said through hole (5.1).

    An advantageous form, as shown in the figures, is that the plastic support sheet (1), the conductive part (3) and the insulating part (4) are quadrangular in shape. Advantageous dimensions are that the plastic support sheet (1) is 35 mm x 10 mm approx., Thickness 0.3 mm approx. Any other form is possible and will depend on the specific needs of the end use: oval, circular, polygonal, etc.

    Similarly, the active part (2) and the through hole (5.1) are circular, mainly derived from the fact that the active part (2) is made by filtering 30 placed in the mouth of a container and the through hole (5.1) will house preferably a drop of sample (6). Advantageous dimensions are that the active part (2) and the orifice (5.1) are, respectively, of diameters 8 and 5 mm approx. Any 35
    Another way is possible and will depend on the final and particular use.

    The method of manufacturing an electrode as mentioned above comprises the following 5 steps:
    a) filtering a dispersion of carbon nanofibers and bismuth nanoparticles on the plastic base (2.1) of the active part (2);
    b) drying of the plastic base (2.1) obtained in 10 a);
    c) fixing the plastic base (2.1) obtained in b) to the plastic support sheet (1) by means of a resin (for example Polymeric Dielectric Materials D2071120D1 of Gwent Group, UK); fifteen
    d) curing of the resin applied in c);
    e) application of the conductive part (3) on the set obtained in d);
    f) curing of the conductive part (3) in e);
    g) application of the insulating part (4) on the assembly obtained in f) by means of a resin (for example Polymeric Dielectric Materials D2071120D1 of Gwent Group, UK);
    h) curing of the resin applied in g);
    i) fixing the plastic mask (5) on the assembly obtained in h) by means of a resin (for example Polymeric Dielectric Materials D2071120D1 of Gwent Group, UK);
    j) curing of the resin applied in i).
     30
    The dispersion of nanofibers is usually done in ethanol and by sonication to achieve an optimal dispersion, as is known.

    Preferably, in step a) first
    filter the dispersion of carbon nanofibers on the plastic base (2.1), normally under vacuum, on the obtained, plastic base (2.1) with carbon nanofibers, the dispersion of bismuth nanoparticles is filtered.
     5
    Specifically and optionally, it is verified that it works optimally that the drying of stage b) is carried out for 12 hours at room temperature; that the curing of step d) is carried out in an oven at 75 ° C for 2 hours; that the conductive part (3) 10 applied in e) comprises silver and is cured in step f) for 30 minutes at 75 ° C; that the curing of step h) is carried out in an oven at 75 ° C for 2 hours; that the curing of step j) is carried out in an oven at 75 ° C for 2 hours. fifteen

    An example of electrochemical measurement is shown in Figure 5 where the conductive part (3) is connected by a cable (9) to a potentiostat, not shown, as well as a reference electrode (7) and an auxiliary 20 (8) by means of their corresponding electric cables (9). The sample (6) is a drop, about 100 µl, arranged in the hole (5.1) of the plastic mask (5), thus being in contact with the active part (2); in said drop the reference electrode (7) and the auxiliary (8) are immersed. Electrochemical scanning is carried out as usual.
    权利要求:
    Claims (15)
    [1]

    1.-Electrode for metal detection in a sample (6) comprising:
    -a plastic support sheet (1); 5
    - an active part (2) arranged on the plastic support sheet (1) and comprising a plastic base (2.1);
    - a conductive part (3) arranged on a portion of the active part (2) and the plastic support sheet (1) extending over 10;
    - an insulating part (4) covering the central area of the plastic support sheet (1) so that a portion of the active part (2) and a portion of the conductive part (3) on the side of the sheet is free (1) opposite the active part (2);
    characterized in that carbon nanofibres (2.2) and bismuth nanoparticles (2.3) are fixed on the plastic base (2.1) of the active part (2), and on the active part (2) a plastic mask 20 (5) is provided. with a through hole (5.1) so that the sample (6) is deposited in said through hole (5.1).
    [2]
    2. Electrode according to claim 1 wherein the plastic support sheet (1) is made of polyethylene terephthalate 25 (PET).
    [3]
    3.-Electrode according to any of the preceding claims wherein the plastic base (2.1) is made of polytetrafluoroethylene (PTFE).
    [4]
    4. Electrode according to any of the preceding 30 claims wherein the conductive part (3) comprises silver (Ag).
    [5]
    5.-Electrode according to any of the
    previous claims wherein the insulating part (4) comprises an epoxy resin with mineral filler.
    [6]
    6. Electrode according to any of the preceding claims wherein the plastic mask (5) comprises polytetrafluoroethylene (PTFE). 5
    [7]
    7. Electrode according to any of the preceding claims wherein the plastic support sheet (1), the conductive part (3) and the insulating part (4) are quadrangular in shape.
    [8]
    8. Electrode according to claim 7 wherein the active part (2) and the through hole (5.1) are circular in shape.
    [9]
    9. Method of manufacturing an electrode according to any of the preceding claims characterized in that it comprises the following steps:
    a) filtering a dispersion of carbon nanofibers and bismuth nanoparticles on the plastic base (2.1) of the active part (2);
    b) drying of the plastic base (2.1) obtained in a);
    c) fixing the plastic base (2.1) obtained in b) 20 to the plastic support sheet (1) by means of a resin;
    d) curing of the resin applied in c);
    e) application of the conductive part (3) on the set obtained in d);
    f) curing of the conductive part (3) in e); 25
    g) application of the insulating part (4) on the assembly obtained in f) by means of a resin;
    h) curing of the resin applied in g);
    i) fixing the plastic mask (5) on the assembly obtained in h) by means of a resin; 30
    j) curing of the resin applied in i).
    [10]
    10. Method according to claim 9 in the
    that in stage a) the carbon nanofiber dispersion on the plastic base is filtered first (2.1), then the dispersion of bismuth nanoparticles is filtered.
    [11]
    11. Method according to any of the 5 claims 9 to 10 wherein the drying of step b) is carried out for 12 hours at room temperature.
    [12]
    12. Method according to any of claims 9 to 11 wherein the curing of step 10 d) is carried out in an oven at 75 ° C for 2 hours.
    [13]
    13. Process according to any of claims 9 to 12 wherein the conductive part (3) applied in e) comprises silver and is cured in step f) for 30 minutes at 75 ° C. fifteen
    [14]
    14. Method according to any of claims 9 to 13 wherein the curing of step h) is carried out in an oven at 75 ° C for 2 hours.
    [15]
    15. Process according to any of claims 9 to 14 wherein the curing of step 20 j) is carried out in an oven at 75 ° C for 2 hours.
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