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    • 专利摘要:
    Resistive sensor for benzene gas detection and procedure for obtaining it. The resistive sensor a includes a support with electrodes coated with functionalized carbon nanotubes and decorated with metallic nanoparticles, whose metallic nanoparticles support a monolayer of an organic compound of the resorcin [4] arene group. A device comprising said resistive sensor a and a resistive sensor b is also protected, as is sensor a, except that it does not include organic compound, to selectively and with a high sensitivity detect benzene gas in air. The device is reversible. The procedure for obtaining the resistive sensor a comprises selecting a support, drawing electrodes, treating the nanotubes with oxygen, decorating them with metallic nanoparticles, depositing the nanotubes on the electrodes; prepare a solution of the organic compound and immerse the support in said solution to form a monolayer of the organic compound. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2574657A1
    申请号:ES201431698
    申请日:2014-11-18
    公开日:2016-06-21
    发明作者:Pierrick CLÉMENT；Eduard Llobet Valero；Enrique José PARRA ARNÓ；Pau BALLESTER；Sasa KOROM
    申请人:Institut Catala dInvestigacio Quimica ICIQ；Institucio Catalana de Recerca i Estudis Avancats ICREA；Universitat Rovira i Virgili URV；
    IPC主号:
    专利说明:

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    DESCRIPTION
    RESISTIVE SENSOR FOR THE DETECTION OF GAS BENZENE AND PROCEDURE
    FOR YOUR OBTAINING
    The present invention is part of the detection of benzene gas.
    The invention relates to a resistive sensor for the detection of benzene gas based on carbon nanotubes. The invention also relates to a device comprising said resistive sensor that has high sensitivity and selectivity to benzene gas. The invention also relates to a method for obtaining said resistive sensor.
    Background of the invention
    Benzene is a non-polar aromatic chemical compound of molecular formula C6H6 and length 5.2 A. Benzene belongs to the group of BTEX compounds that are characterized by the fact that they have similar structures. Said group of BTEX compounds includes benzene, toluene, ethyl benzene and xylene. Benzene is, among volatile organic compounds (VOC), one of the most harmful substances. It is a flammable and toxic vapor recognized as a human carcinogen by the American Environmental Protection Agency or the European Commission. It is known that prolonged exposure to benzene at relatively low concentrations for months or even years generates severe hemotoxic problems such as aplastic anemia and pancytopenia and produces non-lymphocytic leukemia.
    In the last decade, the permitted exposure limit was in the range between 10 ppm and 100 ppb. However, Directive 2008/50 / EC of the Council and European Parliament has established an average annual limit of benzene exposure of 5pg / m3 (1.6 ppb).
    Today there are different methods for detecting traces of benzene. However, these methods require pumping the sample and then analyzing it using micro-chromatographic methods with a preconcentration stage before injection. In these methods it is necessary to use photoionization detectors (PID), whose use is, however, undesirable and high cost for each reading, among other inconveniences.
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    In recent decades, interest in sensors based on carbon nanotubes (CNT) has increased. Thus, for example, US patent application 2007/0237705 discloses a method capable of providing carbon nanotube chains oriented perpendicularly to a substrate, where said carbon nanotube chains have the capacity to adsorb and desorb different types of substances causing diseases, toxic substances or biological substances. In particular, the patent application discloses a method for providing a carbon nanotube chain consisting of a row of carbon nanotubes of 1 micron or less in length, where said carbon nanotube chain is useful as a target target detector. . The carbon nanotube chain may comprise an analyte capture body, whose body comprises a junction portion capable of binding to the carbon nanotube and a target portion capable of capturing the analyte, where said sensor operates based on changes in mass or viscosity when the analyte is captured and said change results in a change in the resonant frequency of the whole. Gas sensing involves transferring the nanotube chains to a resonant transducer type QCM or SAW. Resonant devices are expensive and require an electronic control and measurement of high complexity, high consumption and very difficult miniaturization to make this approach suitable for development in portable devices. You also need a stable environment (without vibration) to make correct measurements.
    Although benzene gas detection devices have been improved, they still have limitations in the response time, energy consumption to desorb the analyte, the cost in its manufacture and sample analysis, among others.
    The petrochemical industry has been claiming for years a portable sensor device capable of working continuously, capable of detecting benzene gas selectively and in real time at reduced concentrations. A portable sensor device capable of quantifying in real time the concentration of benzene gas present in the working atmosphere of the operators is especially desirable. However, there is still no such sensor device.
    Therefore, there is a need to find new devices for the detection of benzene gas that allow the detection of the presence of benzene gas at reduced concentrations even in the presence of other BTEX compounds or other contaminants, which provides a real-time response, which present high sensitivity and selectivity to
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    benzene gas and allow quantifying its concentration. It is also desirable to provide a sensor device that is reversible, with low energy consumption for desorption and that can be manufactured with low cost consumables.
    Description of the invention
    With the resistive sensor for the detection of benzene gas of the invention, the aforementioned drawbacks are resolved, also presenting other advantages that will be described below.
    In the present invention, the term "resistive sensor" means a sensor whose electrical resistance exhibits measurable variations in the face of variations in the surrounding gas concentration.
    In a first aspect, the invention provides a resistive sensor A for the detection of benzene gas comprising a dielectric support with electrodes coated with carbon nanotubes, characterized by the fact that said carbon nanotubes are functionalized with carbonyl and carboxyl groups. and they are decorated with metal nanoparticles, whose metal nanoparticles support a monolayer of an organic compound of the resorcin [4] sand group.
    Advantageously, with the resistive sensor A according to the first aspect of the present invention it is possible to detect the presence of traces of benzene gas and quantify its concentration in real time. In addition, it presents total reversibility of the absorption and desorption stages, at room temperature, with reduced energy consumption.
    Carbon nanotubes can be single or multi-wall carbon nanotubes, functionalized with carbonyl and carboxyl groups. Carbon nanotubes act as signal transducers.
    The metal nanoparticles can be of any noble metal. Preferably, the metal nanoparticles are of a metal selected from Au and Ag.
    The particle size of the metal nanoparticles is not limited in the present invention, although for them to be easily anchored in the carbon nanotubes a particle size between 1 and 50 nm is preferable.
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    The same applies to the shape of the nanoparticle that can be any such as, for example, cylindrical, triangular, pyramidal, cubic, spherical, star shape, rod shape or a combination thereof, although a spherical shape is preferable.
    The organic compound of the resorcin [4] arene group, also referred to in the present cavitant invention (I), has the general formula (I):
    image 1
    X2
    where:
    R1 is selected from a radical of formula -R2-S-R3, -R2-SS-R3, or -R2-R5, where R2 means C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkynyl;
    R3 means H, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, or -COR2, where R2 has the same above meaning;
    R5 is a lipoate radical;
    R4 is selected from H, C1-C20 alkyl, C1-C6 alkyloxy, halosubstituted C1-C6 alkyl, halogen (I, Cl, F, Br), cyano (-CN) and nitro (-NO2);
    l, m and n independently mean an integer selected between 0 and 1, where at least one of l, m or n is 1, and when l is 0, then O atoms adjacent to X2 carry hydrogen atoms; and when m is 0, then O atoms adjacent to X3 carry hydrogen atoms; and when n is 0, then O atoms adjacent to X4 carry hydrogen atoms;
    X1, X2, X3 and X4 are the same or different and are each a divalent radical selected
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    Among the group consisting of:
    - Ci-Ca alkyl;
    - Ca-C20 mono or polyclide hydrocarbon of 1 to 3 isolated cycles, partially or totally
    condensates, where each of the cycles can be independently
    unsaturated aromatic or alicyclic, the cycle being unsubstituted or substituted by a radical selected from C1-C20 alkyl, Ci-Ca alkyloxy, halosubstituted Ci-Ca alkyl, halogen, cyano and nitro; or
    - C5-C20 mono or polyclide hydrocarbon of 1 to 3 isolated cycles, partially or totally
    condensates, where each of the cycles can be independently
    aromatic or unsaturated alicyclic, with at least one cycle with one or more heteroatoms as a member (s) of the cycle independently selected from O, S and N, the cycle being unsubstituted or substituted by a radical selected from C1-C20 alkyl, CrCa alkyloxy , halosubstituted CrCa alkyl, halogen, cyano and nitro.
    The organic compound of the resorcin [4] arene or cavitant group of general formula (I) acts as a receptor ("host") of the benzene molecule, and is attached to the metal nanoparticle by the S atom or atoms of R1.
    The resistive sensor A according to the first aspect of the present invention is capable of operating at ambient temperature and pressure.
    The resistive sensor A according to the first aspect of the present invention is
    capable of detecting the presence of benzene gas in real time, that is, it does not require
    processes or stages of concentration or treatment of the sample to provide a reading of the presence of benzene gas.
    Ace! therefore, the resistive sensor A according to the first aspect of the present invention has high sensitivity to benzene, detecting the presence of benzene gas at concentrations below 50 ppb, concentrations below 30 ppb, concentrations below 10 ppb, up to a threshold with a lower detection limit of 600 ppt.
    The authors of the present invention theorize that the operating mechanism of the resistive sensor A according to the first aspect of the present invention could be based on the fact that the benzene molecule trapped in the cavity of the cavitant (l) increases the apparent density of the aromaticity of the cavitant (I) which affects the carbon nanotubes by proximity. The aromatic structures referred to both the walls of the
    to
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    cavitant (I) as the benzene molecule trapped by the cavitant (I) are rich in electrons and the change produced by the absorption of the benzene molecule affects the density of states (DOS) and displaces the position of the Valencia band of carbon nanotubes, away from Fermi level. This causes a decrease in the number of holes (free-charge carriers), which translates into a decrease in conductance.
    In a second aspect, the invention provides a device comprising resistive sensor A in accordance with the first aspect of the invention.
    The device according to the second aspect further comprises at least one resistive sensor B that includes a dielectric support with electrodes coated with carbon nanotubes functionalized with carbonyl and carboxyl groups and decorated with metal nanoparticles, and does not include organic compound, where the resistive sensor B does not react in the presence of benzene gas.
    In the present invention, the expression "does not react in the presence of benzene gas" means that the sensor does not modify its resistivity when exposed in an atmosphere that includes benzene gas, and the expression "reacts in the presence of benzene gas" means that the sensor modifies its resistivity when exposed in an atmosphere that includes benzene gas. The same is interpreted when the expression refers to whether it reacts or does not react in the presence of nitrogen dioxide and / or ozone, but in this case the sensor is exposed in an atmosphere that includes nitrogen and / or ozone dioxide gas.
    Advantageously, the device according to the second aspect of the invention is capable of operating in the air and in oxidizing atmospheres and at the same time being extremely selective to benzene gas even in the presence of other BTEX compounds. The resistive sensor B is different from the resistive sensor A only because it does not contain the monolayer of the organic compound of the resorcin [4] sand or cavitant group (I). Advantageously, the resistive sensor B does not react in the presence of benzene gas and, however, has high sensitivity or reacts in the presence of nitrogen dioxide and / or ozone.
    Surprisingly, the presence of metal nanoparticles in the configuration of the resistive sensor B, which does not carry cavitant (I), unexpectedly increases the sensitivity of the resistive sensor B to nitrogen dioxide and / or ozone, which makes it possible to compensate for any reaction
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    of the resistive sensor A with the nitrogen dioxide and / or ozone, and in turn allows to further increase the selectivity of the resistive sensor A to benzene gas.
    The presence of metal nanoparticles in the configuration of the resistive sensor A also further increases the sensitivity of the resistive sensor A to benzene gas, allowing a configuration containing at least one resistive sensor A and at least one resistive sensor B a significant increase in sensitivity and of the selectivity of detection of benzene gas in air or an oxidizing atmosphere even containing compounds of the BTEX group.
    Advantageously, the device according to the second aspect of the present invention is reversible. By exposing the device in an environment with the presence of benzene gas, the cavitants anchored in the metal nanoparticles forming a monolayer capture the benzene molecules from the environment. This capture or absorption is done through a weak interaction (fisisorption) between the cavitant and the benzene molecule. It seems that a balance is established between atmospheric free benzene and captured benzene. This equilibrium is dynamic, so that by adding a benzene gas-free air flow, the conductance or resistance of the carbon nanotube layer recovers its initial value by providing as! a sensor with reversibility properties.
    The device according to the second aspect of the present invention further comprises for each resistive sensor (A, B) a microelectronic circuit for receiving and / or processing the electrical signal of the electrodes of each resistive sensor (A, B), and a transmitter to send the data obtained by each resistive sensor (A, B) to a remote receiver.
    The invention also relates to the use of the device for the detection of benzene gas.
    In a third aspect, the invention provides a method for obtaining the resistive sensor A for the detection of benzene gas according to the first aspect of the invention, which is characterized by the fact that it comprises the following steps:
    - select a dielectric support;
    - draw on said support a pair of electrodes with the desired design;
    - treating carbon nanotubes with oxygen to give carbon nanotubes functionalized with carbonyl and / or carboxyl groups;
    - decorate carbon nanotubes with metal nanoparticles;
    - deposit the carbon nanotubes on the electrodes as a coating, where the carbon nanotubes are interchangeably decorated with the nanoparticles
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    before or after depositing on the electrodes;
    - preparing a solution of an organic compound of the resorcin [4] arene group;
    - submerge the dielectric support with electrodes coated with carbon nanotubes functionalized with carbonyl and carboxyl groups and decorated with metal nanoparticles in the solution prepared to join the organic compound of the resorcin group [4] arene in solution to the metal nanoparticles and form a monolayer as a coating.
    Advantageously, a process is provided that uses low cost materials and technology compared to those used to manufacture the state of the art sensors.
    The obtaining of the resistive sensor B comprises the same steps defined for obtaining the resistive sensor A with the exception of the stage relative to the organic compound of the resorption group [4] sand.
    The dielectric support is of a material not limited in the present invention, although a material selected from the group comprising a flexible polymer, a ceramic material such as, for example, alumina, oxidized silicon or sapphire, is preferable.
    The electrodes can be drawn by any conventional technique used for that purpose. Serigraph, evaporation, cathode pulverization or injection printing is preferred. The electrodes may be of any material intended for that purpose that are within the reach of a person skilled in the art. Platinum electrodes (Pt) are preferred.
    Carbon nanotubes are treated with oxygen by radiofrequency cold plasma or by a wet chemical process. As a result of the reaction of oxygen with the carbon atoms of the chains that make up the carbon nanotubes, these are functionalized with carbonyl and carboxyl groups.
    Carbon nanotubes are decorated with metal nanoparticles by evaporation, cathode spray, chemical deposition in vapor phase or a colloidal solution of said nanoparticles in a radiofrequency plasma.
    Carbon nanotubes can be deposited on the electrodes by any conventional technique for that purpose. The technique of electrodeposition, injection printing, drip coating, screen printing or airbrushing is preferred.
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    The preparation of the solution comprises diluting in an aprotic polar solvent an amount of the organic compound of the resorcin [4] arene group, so that the concentration of the organic compound in solution is between 0.5 and 1 mmol / L.
    The organic compound of the resorcin [4] arene group is attached to the metal nanoparticles by the known technique of self-assembled monolayer (SAM) for the appropriate time and temperature, followed by drying or evaporation of the solvent. Surprisingly, said organic compound of the resorcin [4] arene group is capable of absorbing benzene gas molecules through the cavity that defines the resorcin [4] arene. The organic compound of the resorcin [4] arene group has the general formula (I) defined above, whose preferred embodiments are included herein with reference to the content described in the first aspect of the invention.
    The obtaining of single or multipared carbon nanotubes is not part of the scope of the present invention, as is the obtaining of the organic compound of the resorption group [4] arene of general formula (I) or the obtaining of the metal nanoparticles, which they can be obtained from any conventional method available to a person skilled in the art.
    Brief description of the figures
    For a better understanding of how much has been exposed, some drawings are combined in which, schematically and only by way of non-limiting example, a practical case of realization is represented.
    Figure 1 shows a schematic drawing of multipared carbon nanotubes (3) decorated with gold nanoparticles (4) to which the cavitant (I) joins to form a continuum of these junctions a caperer monolayer (5) (I) supported on the gold nanoparticles (4), in a resistive sensor A. Neither the dielectric support (1) nor the electrodes (2) are shown.
    Figure 2 (a) shows a graph of the resistance changes of a device according to the invention comprising a resistive sensor A and a resistive sensor B as a function of the concentration of benzene gas in air at 400 ml / min. The resistive sensor A includes a cavitant of formula (I4); gold metal nanoparticles (Au); and carbon nanotubes
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    multipared functionalized with carbonyl and carboxyl groups [cavitant (U) @ Au / O-MWCNTs] and the resistive sensor B does not include cavitant but if gold metallic nanoparticles (Au) and multipared carbon nanotubes functionalized with carbonium and carboxyl groups [Au / O- MWCNTs]. Figure 2 (b) shows the relative response expressed as a percentage [SR (%)] of the device at different gas flow rates, where - • - means a flow rate of 100 ml / min, - ■ - means a flow rate of 200 ml / min and - ▲ - means a flow rate of 400 ml / min as a function of the benzene concentration expressed in ppb.
    Figure 3 shows a graph of the resistance changes of a device according to the invention comprising a resistive sensor A [cavitant (L) @ Au / O-MWCNTs] and a resistive sensor B [Au / O-MWCNTs] as a function of Benzene concentration In said figure 3 it can be observed that despite detecting concentrations eight times higher between two different cycles, the reproducibility of the device is not affected.
    Detailed description of the invention
    The resistive sensor A for the detection of benzene gas includes a monolayer 5 of an organic compound of the resorcin group [4] arene of general formula (I) included above.
    Next, preferred embodiments of the organic compound of the resorcin [4] arene group are included, where otherwise specified, R1, R2, R3, R4, R5, 1, m, n, Xi, X2, X3, X4, they have the meaning included above in the general formula (I).
    In a preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from the groups of formula -R2-S-R3 and -R2-SS-R3.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from a radical of the formula -R2-S-R3, or -R2-SS-R3, where R2 means C1-C20 alkyl and R3 means C1-C20 alkyl or H.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 mean C4-C12 alkyl.
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    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is a radical of the formula -R2-S-R3, where R2 and R3 mean decanoyl.
    In a preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R4 is H.
    In a preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where X1, X2, X3, X4 are the same.
    In a preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where l, m and n are 1.
    In a preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where X1, X2, X3 and X4 are each a divalent radical selected from the group consisting of:
    - CrCa alkyl;
    - C6-C20 mono- or polyclide hydrocarbon of 1 to 2 isolated cycles, partially or totally doomed, where each cycle can be independently aromatic or unsaturated alicyclic; more preferably, a mono or C6-C20 polycarbon hydrocarbon of 1 to 2 isolated cycles, partially or totally condemned, where each of the cycles is aromatic; or
    - C5-C20 mono or polyclide hydrocarbon of 1 to 2 isolated cycles, partially or fully condensed, where each of the cycles can be independently aromatic or unsaturated alicyclic with at least one cycle containing one or four heteroatoms as member (s) of the cycle independently selected from O, S and N; more preferably, a C5-C20 mono or polyclide hydrocarbon of 1 to 2 isolated, partially or fully condensed cycles, where each of the cycles can be independently aromatic or unsaturated alicyclic with at least one cycle that
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    it contains one or two heteroatoms as a member (s) of the cycle independently selected from O, S and N; even more preferably, a C5-C20 mono or polydial hydrocarbon of 1 to 2 isolated, partially or fully condensed cycles, where each of the cycles is aromatic with at least one cycle containing one or two heteroatoms as a member (s) of the independently selected cycle between O and N.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where Xi, X2, X3 and X4 are each a divalent radical selected from the group consisting of:
    methane, ethane, cyclohexane, dihydronaphthalene, benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, naphthyridine, pyrazine, quinoxaline, benzoxazole, quinazoline, cinnitroline; more preferably, ethane, cyclohexane, dihydronaphthalene, benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, naphthyridine, pyrazine, quinoxaline, benzoxazole, quinazoline, cinn.
    In another more preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where Xi, X2, X3 and X4 are each a divalent radical selected from the group consisting of:
    image2
    image3
    In another more preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where Xi, X2, X3 and X4 are each methylene or a divalent radical of formula (Ilc).
    In a preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R4 is H; and l, m, and n are 1.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
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    R4 is H;
    l, m, and n are 1; Y
    Xi, X2, X3 and X4 are the same and are each a divalent radical derived from the group consisting of:
    methane, ethane, cyclohexane, dihydronaphthalene, benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, naphthyridine, pyrazine, quinoxaline, benzoxazole, quinazoline, cinnitroline; more preferably, ethane, cyclohexane, dihydronaphthalene, benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, naphthyridine, pyrazine, quinoxaline, benzoxazole, quinazoline, cinn.
    In yet another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R4 is H;
    l, m, and n are 1; Y
    Xi, X2, X3 and X4 are the same and are each methylene or a divalent radical of formula (Ila), (llb), (llc), (lld), (lle), and (Ilf):
    image4
    image5
    In yet another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (1) where:
    R4 is H;
    l, m, and n are 1; Y
    Xi, X2, X3 and X4 are the same and are each methylene or a radical of formula (llc).
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (1) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H; and l, m, and n are 1.
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    In another preferred embodiment, the organic compound of the resorcin [4] arene group has a general formula (I) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 are decanoyl;
    R4 is H; and l, m, and n are 1.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H;
    l, m, and n are 1; Y
    X1, X2, X3 and X4 are the same and are each a divalent radical derived from the group consisting of:
    methane, ethane, cyclohexane, dihydronaphthalene, benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, naphthyridine, pyrazine, quinoxaline, benzoxazole, quinazoline, cinnitroline; more preferably, ethane, cyclohexane, dihydronaphthalene, benzene, naphthalene, anthracene, phenanthrene, furan, thiophene, indole, benzofuran, benzothiophene, quinoline, isoquinoline, naphthyridine, pyrazine, quinoxaline, benzoxazole, quinazoline, cinn.
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H;
    l, m, and n are 1; Y
    X1, X2, X3 and X4 are the same and are each methylene or a divalent radical of formula (IIa), (IIb), (IIc), (Ild), (Ile), and (IIf):
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    image6
    image7
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is selected from a radical of formula -R2-S-R3, or -R2-SS-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H;
    l, m, and n are 1; Y
    Xi, X2, X3 and X4 are the same and are each methylene or a radical of formula (IIc).
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is a radical of formula -R2-S-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H;
    l, m, and n are 1; Y
    X1, X2, X3 and X4 are the same and are each methylene or a radical of formula (IIc).
    In another preferred embodiment, the organic compound of the resorcin [4] arene group has the general formula (I) where:
    R1 is a radical of formula -R2-S-R3, where R2 and R3 are decanoyl;
    R4 is H;
    l, m, and n are 1; Y
    X1, X2, X3 and X4 are the same and are each methylene or a radical of formula (IIc).
    In yet another embodiment, the organic compound of the resorcin [4] arene group has the formula (I4):
    image8
    In yet another preferred embodiment of the present invention, the organic compound of the resorcin [4] arene group has the formula (I5):
    image9
    5 By way of non-limiting example of the present invention, a synthesis scheme is included for the preparation of an organic compound of the resorption group [4] arene of general formula (I):
    image10
    1, step 2 is carried out with at least 4 equivalents of reagent XX5X6.
    5 In the section of the examples of the invention the obtaining of the organic compounds of the resorcin group [4] arene of formulas (I4) and (I5) is exemplified.
    Preferably, the metal nanoparticles 4 are gold nanoparticles. Preferably, the particle size of the metal nanoparticles 4 is between 1 and 10 nm. 10 Also preferably, the metal nanoparticles 4 have a spherical or spheroidal shape.
    Preferably, carbon nanotubes 3 are multi-wall carbon nanotubes. Preferably, the 3 multipared carbon nanotubes have an average length of 15 to 1.5 mm and an average diameter of up to 9.5 nm.
    In a preferred embodiment of the first aspect of the present invention, the resistive sensor
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    A presents the following configuration: a dielectric support 1 with electrodes 2 coated with carbon nanotubes 3 multipared functionalized with carbonyl and carboxyl groups and decorated with metal nanoparticles 4 of gold of size between 1 and 10 nm and spherical shape, whose metal nanoparticles 4 support a monolayer 5 of an organic compound of the resorcin [4] arene group of general formula (I):
    image11
    X2
    where
    R1 is a radical of formula -R2-S-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H;
    l, m, and n are 1; Y
    X1, X2, X3 and X4 are the same and are each methylene or a divalent radical selected from the group consisting of:
    image12
    image13
    image14
    N
    image15

    image16
    N
    image17

    (lla) (Hb) (Me) (lid)
    preferably, the divalent radical of formula (Ilc).
    (Ilf)
    image18
    Advantageously, said configuration of the resistive sensor A is capable of detecting benzene gas with a lower detection limit of 600ppt.
    Preferably, the resistive sensor A comprises a dielectric support 1 of alumina and platinum electrodes 2.
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    In a preferred embodiment of the second aspect of the present invention, the device comprises at least one resistive sensor A that includes a dielectric support 1 with electrodes 2 coated with multipared carbon nanotubes 3 functionalized with carbonyl and carboxyl groups and decorated with gold nanoparticles 4 , whose metal nanoparticles support a monolayer 5 of an organic compound of the resorcin group [4] aren as a coating, and comprises at least one resistive sensor B that includes a dielectric support 1 with electrodes 2 coated with multipared carbon nanotubes 3 functionalized with carbonyl and carboxyl groups and decorated with 4 gold nanoparticles, not including the organic compound resistive sensor B.
    For a reading of the presence of benzene gas, the device also comprises for each resistive sensor (A, B) a microelectronic circuit to receive and / or process the electrical signal of the electrodes of each resistive sensor (A, B), and a transmitter to send the data obtained by each resistive sensor (A, B) to a remote receiver.
    In the preferred configuration of the device according to the second aspect of the invention, the presence of at least one resistive sensor B, as defined herein, which has the condition of not being sensitive or not reacting with benzene but if reacts in the presence of oxidizing gases such as nitrogen and / or ozone dioxide, provides, in the presence of a resistive sensor A, as defined here, high sensitivity and selectivity to benzene gas in air or oxidizing atmospheres, not interfering with the presence of BTEX group compounds in the sensitivity, or benzene selectivity of the device.
    In addition, advantageously, a device with real-time benzene gas detection and with benzene gas detection is provided despite being present at reduced concentrations. Advantageously, the device has a high sensitivity that can reach a lower detection limit of 600 ppt. Advantageously, the device is capable of detecting concentrations of benzene in air of values greater than or equal to the lower limit of detection.
    Surprisingly, the metal nanoparticles 4, preferably gold, both in the resistive sensor A and the resistive sensor B unexpectedly further increase the detection sensitivity of the sensors involved in the device, also increasing the selectivity to benzene gas.
    Advantageously, the device according to the second aspect of the invention is
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    capable of being manufactured on a micrometric scale and in portable mode. The device of the invention is capable of working continuously and is useful for the detection of benzene gas in an atmosphere of oxidizing gases such as, for example, nitrogen dioxide and / or ozone.
    In a preferred embodiment of the third aspect of the present invention, the method comprises the following steps:
    - select a dielectric support 1 of alumina;
    - drawing on said support a pair of electrodes 2 of Pt with the desired design;
    - Treat the carbon nanotubes 3 multipared with oxygen by bombardment by a cold plasma radio frequency of Ar;
    - deposit the carbon nanotubes 3 multipared by airbrush on the electrodes 2 as a coating and before decorating the nanotubes with the gold metallic nanoparticles 4;
    - decorate 3 multipared carbon nanotubes with 4 gold metallic nanoparticles by cathode spraying;
    - preparing a solution of an organic compound of the resorcin [4] arene group of general formula (I), preferably of formula (I4) or (I5);
    - immersing in said solution the dielectric support with electrodes coated with multipared carbon nanotubes 3 functionalized with carbonyl and carboxyl groups and decorated with gold metal nanoparticles 4 to form a monolayer 5 as an organic compound coating.
    Advantageously, the immersion in the solution is maintained for a period between 12 and 36h, at a temperature between 40 and 80 ° C.
    In a preferred embodiment, the preparation of the solution comprises diluting in a halogenated solvent, still more preferably in chloroform or dichloromethane, and even more preferably in chloroform, an amount of the organic compound of the resorption group [4] arene of general formula (I) , so that the concentration of the organic compound in solution is between 0.5 and 1 mmol / L.
    The fabrication of the resistive sensor B comprises the same steps as for the fabrication of the resistive sensor A, with the only exception that the stages relating to the formation of a monolayer 5 of the organic compound of the resorption group [4] are not included in the manufacturing of resistive sensor B because this resistive sensor B does not include organic compound.
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    Examples
    Preparation of a resistive sensor A and a resistive sensor B, without organic compound
    The multipared carbon nanotubes (MWCNTs of Nanocyl ™, quality 3101) were grown by chemical deposition in vapor phase with a purity greater than 95% of carbon after a functionalization with oxlqen of its surface by means of the radiofrequency cold plasma technique ( O-MWCNTs). The nanotubes grew 1.5 pm in average length and 9.5 nm in average diameter. The objective to functionalize was to clean the amorphous carbon carbon nanotubes and create reactive sites (i.e. oxygenated vacancies) in which metal nanoparticles can nuclear. The O-MWCNTs were suspended in 0.5% w / w chloroform and sonicated for 30 min to disperse them evenly in the solution. The prepared suspension was deposited by aeroqrafla on a ceramic substrate (alumina) with platinum electrodes (inter-electrode spacing of 500 pm) drawn by seriqrafla, during deposition, said substrate was preheated to 100 ° C (for rapid elimination of the solvent). A control of the resistance of the carbon nanotube layer was maintained during deposition in order to reach a predefined value of 5 kQ to provide operability in the defined resistance range (low noise, control of the amount of carbon nanotubes deposited ).
    The treated O-MWCNTs were decorated using the radio frequency cathode spray technique at 13.56 MHz in Ar plasma at 0.1 Torr and room temperature with an energy of 30 W for 10 seconds.
    Formation stage of a monolayer 5 of the organic compound of the resorcin group [4] arene for the resistive sensor A
    A, continuation, for the resistive sensor A, a stage of formation of a monolayer of the organic compound of the resorption group [4] sand was additionally carried out. For the formation of said monolayer, the self-assembled monolayer technique SAM was followed.
    For the formation of the monolayer, the dielectric support containing interdiqited electrodes coated with multipared carbon nanotubes decorated with gold nanoparticles prepared above in a solution of the resorcin [4] arene (I4) in 0.5 mM chloroform was submerged. The interaction with the gold nanoparticles was achieved through
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    the union of the four central thioether functional groups of the compound of formula (I4). The SAM process was carried out for 24 hours at 60 ° C. These conditions allowed an ordered deposition of the compound of formula (I4) on the metal nanoparticles (Au). Finally, the support was removed, cooled to room temperature, rinsed with pure chloroform and dried at 50 ° C for 30 min.
    Sensing properties of the device comprising resistive sensor A and resistive sensor B
    The gas sensing properties of the device obtained were measured using a miniaturized Teflon chamber. The mass flow rate was controlled by computer (Bronkhorst hi-tech 7.03.241) and calibrated gas bottles (NO2, CO, Ethanol, Benzene, Toluene, or xylene all diluted in Praxair dry air; 99.99%) were used, and Air Products dry air. Additionally, the gas mixture could have been humidified to controlled humidity levels using a liquid mass flow controller. A continuous flow rate (100-200 and 400 mL.min-1) was used in all measurements. The device, once placed inside the test chamber, was connected to a multimeter interface, which allowed a real-time resistance reading of the device response with an SR% = (Rgas - Raire) * 100 / Raire. During all tests, which include different response / recovery cycles, the temperature of the experiment was maintained at 25 ° C (See, Figure 2b).
    Synthesis and characterization of the cavitants (I1-5) represented in the above synthesis scheme
    All reagents and solvents were obtained from commercial suppliers and were used without further purification, unless specifically indicated. The 1H NMR spectrum was recorded on a Bruker Avance 400 spectrometer or a Bruker Avance 500. All deuterated solvents (Sigma-Aldrich) were used without further purification. The chemical shifts are given in ppm and the peaks are referenced to the peak of the residual solvent (5acetone = 2.04 ppm, 5CDCl3 = 7.24 ppm). All NMR J values are given in Hz and have not been corrected. All MS were registered in a Bruker MALDI-TOF Autoflex.
    Reaction 1: In a 25 ml two-neck round bottom flask, 2,000 g (17.80 mmol) of resorcinol were dissolved in 15 ml of absolute ethanol, followed by the addition of 6 ml (72.50 mmol) of hydrochloric acid at 37% The reaction mixture was stirred and then
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    added 4 ml dropwise (18.97 mmol) of undec-10-enal. The reaction was stirred at 60 ° C for 24 h. The hot red oil was slowly poured into vigorously stirred water, the precipitate was filtered, washed with boiling water until pH 7 and absence of the characteristic aldehldo (odor). A pale yellow solid of cavitant 1 was dried under vacuum for 24 h. Yield 3.842 g (3.69 mmol, 83%). 1H NMR (500 MHz, Acetone-d6) 5 8.46 (s, 8H), 7.53 (s, 4H), 6.23 (s, 4H), 5.81 (ddt, J = 17.0, 10.2, 6.7 Hz, 4H), 4.98 (ddt, J = 17.1, 2.3, 1.6 Hz, 4H), 4.90 (ddt, J = 10.2, 2, 3, 1.2 Hz, 4H), 4.30 (t, J = 7.9 Hz, 4H), 2.28 (q, J = 7.8 Hz, 8H), 1.43 - 1.26 ( m, 56H). ESI-MS (+): m / z calculated for C68H96O8 + Na + 1063,7003, found 1063,6991.
    Reaction 2: 1,500 g (1.44 mmol) of cavitant 1 was dissolved in 15 ml of dry THF and cooled to -25 ° C. To this solution was added 1.65 ml (13.00 mmol) of chlorotrimethylsilane and then 3.00 ml (21.52 mmol) of triethylamine. The solution was allowed to warm to room temperature and stirred overnight. The solvent was removed and the residue suspended in hexanes and the solid by-product were separated. The hexane was evacuated and the product was purified by flash chromatography on silica eluting with a mixture of methylene chloride and hexanes (8: 2) to give a pale yellow solid product of low melting point. After evacuation in vacuo overnight, 2 was obtained in a yield of 1,976 g (1.22 mmol, 85%). 1H NMR (400 MHz, Chloroform-d) 5 7.11 (s, 2H), 6.23 (s, 2H), 6.13 (s, 2H), 5.95 (s, 2H), 5.77 (ddt, J = 16.9, 10.2, 6.7 Hz, 4H), 4.95 (dq, J = 17.1, 1.6 Hz, 4H), 4.89 (ddt, J = 10 , 2, 2.2, 1.1 Hz, 4H), 4.37-4.31 (m, 4H), 1.99 (q, J = 6.8 Hz, 8H), 1.76 (s, 4H), 1.65 (s, 4H), 1.38-1.07 (m, 52H), 0.33 (s, 40H), -0.05 (s, 32H).
    Reaction 3: In a 5 ml flask under nitrogen, 390.4 mg (241 pmol) of cavitant 2 was dissolved in 2.70 ml of dry THF and the solution was cooled to -60 ° C. Next, 1.95 ml (975 pmol) of 0.5 M 9-borabicide (3.3.1) nonane was added, the solution was stirred allowing the formation of a rosacea solution and 1.95 ml (8.85 was added mmol) of decanetiol. The reaction was allowed to warm to room temperature and stirred for two days. The solvent was evacuated in vacuo, the crude was dissolved in 20 ml of methylene chloride and washed three times with water. The solution was dried over anhydrous sodium sulfate, the solvent was evacuated in vacuo and the product (3) was recrystallized from ethanol as a white solid. The yield was 312 mg (194 pmol, 80%). 1H NMR (500 MHz, Chloroform-d) 5 9.59 (bs, 4H), 9.31 (bs, 4H), 7.17 (bs, 4H), 6.09 (bs, 4H), 4.28 (bt, 4H), 2.47 (td, J = 7.6, 2.6 Hz, 16H), 2.19 (bm, 8H), 1.61 - 1.48 (m, 16H), 1, 41 - 1.19 (m, 112H), 0.86 (t, J = 7.0 Hz, 12H).
    Reaction 4: In a 25 ml Schlenk flask, 500.0 mg (288 pmol) of cavitant 3, 387.0 mg (1.94 mmol) of 2,3-dichloroquinoxaline and 688.0 mg (2) were evacuated in vacuo , 02 mmol) of
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    Cesium carbonate at 60 ° C for one hour and then purged with nitrogen. 17 ml of anhydrous DMF was added and the reaction was carried out under nitrogen, at room temperature overnight and then at 60 ° C for 2 days. The reaction mixture was poured into ice-water and the pale brown precipitate was collected by filtration and rinsed with water. The solid product was extracted with methylene chloride, washed with water, dried over anhydrous sodium sulfate and the solvent was evacuated in vacuo. The crude was purified by flash chromatography on silica, using a gradient of ethyl acetate in methylene chloride, first 2% increasing the gradient to 10% to give colorless flakes of cavitant 4 in a yield of 412.4 mg (184 pmol, 63.9%). 1H NMR (300 MHz, Chloroform-d) 5 8.13 (s, 4H), 7.77 (dd, J = 6.4, 3.4 Hz, 8H), 7.45 (dd, J = 6, 3, 3.5 Hz, 8H), 7.18 (s, 4H), 5.55 (t, J = 7.9 Hz, 4H), 2.49 (t, J = 7.2 Hz, 16H) , 2.33 - 2.11 (m, 8H), 1.63 - 1.48 (m, 16H), 1.48 - 1.11 (m, 112H), 0.91 - 0.80 (m, 12H).
    Reaction 5: In a 25 ml pressure vessel and under a nitrogen atmosphere, 200.0 mg (124 pmol) of cavitant 3 and 260 pL (4.00 mmol) of bromochloromethane were dissolved in 10 ml of dry DMF. Once the solid dissolved, 160 mg (1.16 mmol) of dry potassium carbonate was added, the vessel was sealed and the reaction was carried out at 70 ° C for 24 h. The cooled solution was poured into a 1 M aqueous hydrochloric acid solution and the product was extracted with methylene chloride, dried and the solvent was evacuated in vacuo. The product was recrystallized from diisopropyl ether to give a cavitant 5 in the form of a white solid. The yield was 139.0 mg (84 pmol, 67.5%). 1H NMR (500 MHz, Chloroform-d) 5 7.08 (s, 4H), 6.46 (s, 4H), 5.72 (d, J = 7.2 Hz, 4H), 4.70 (t , J = 8.1 Hz, 4H), 4.41 (d, J = 7.2 Hz, 4H), 2.55 - 2.38 (m, 16H), 2.20 (q, J = 7, 9 Hz, 8H), 1.55 (p, J = 7.4 Hz, 16H), 1.30 (dd, J = 45.5, 8.3 Hz, 112H), 0.86 (t, J = 7.0 Hz, 12H).
    Although reference has been made to a specific embodiment of the invention, it is obvious to one skilled in the art that the resistive sensor A, the device containing it and the method for obtaining the resistive sensor A described in the invention is susceptible of numerous variations and modifications, and that all the mentioned details can be replaced by other technically equivalent ones, without departing from the scope of protection defined by the appended claims.
    权利要求:
    Claims (20)
    [1]
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    1. Resistive sensor (A) for the detection of benzene gas that includes a dielectric support (1) with electrodes (2) coated with carbon nanotubes (3), characterized by the fact that said carbon nanotubes (3) are functionalized with carbonyl and carboxyl groups and are decorated with metal nanoparticles (4), whose metal nanoparticles support a monolayer (5) of an organic compound of the resorcinum group [4] arene.
    [2]
    2. Sensor according to claim 1, wherein the organic compound of the resorcin group [4] arene has the general formula (I)
    image 1
    X2
    where:
    R1 is selected from a radical of formula -R2-S-R3, -R2-SS-R3, or -R2-R5, where R2 means C1-C20 alkyl, C2-C20 alkenyl or C2-C20 alkynyl;
    R3 means H, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, or -COR2, where R2 has the same above meaning;
    R5 is a lipoate radical;
    R4 is selected from H, C1-C20 alkyl, C1-C6 alkyloxy, halosubstituted C1-C6 alkyl, halogen, cyano and nitro;
    l, m and n independently mean an integer selected between 0 and 1, where
    minus one of l, m or n is 1, and when l is 0, then the atoms of O adjacent to
    X2 carry hydrogen atoms; and when m is 0, then the atoms of O adjacent to X3
    they carry hydrogen atoms; and when n is 0, then the atoms of O adjacent to X4
    they carry hydrogen atoms;
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    Xi, X2, X3 and X4 are the same or different and are each a divalent radical selected from the group consisting of:
    - Ci-Ca alkyl;
    - Ca-C20 mono or polycyclic hydrocarbon of 1 to 3 isolated cycles, partially or totally condemned, where each of the cycles can be independently aromatic or unsaturated alicyclic, the cycle being unsubstituted or substituted by a radical selected from C1-C20 alkyl , Ci-Ca alkyloxy, halosubstituted Ci-Ca alkyl, halogen, cyano and nitro; or
    - C5-C20 mono or polyclide hydrocarbon of 1 to 3 isolated cycles, partially or fully condensed, where each of the cycles can be independently aromatic or unsaturated alicyclic, with at least one cycle with one or more heteroatoms as member (s) of the cycle independently selected from O, S and N, the cycle being unsubstituted or substituted by a radical selected from C1-C20 alkyl, CrCa alkyloxy, halosubstituted CrCa alkyl, halogen, cyano and nitro.
    [3]
    3. Resistive sensor (A) according to claim 2, wherein for the compound of general formula (I):
    R4 5 is H and l, m, and n are 1.
    [4]
    4. Resistive sensor (A) according to claim 2, wherein for the compound of general formula (I):
    R1 is a radical of formula -R2-S-R3, where R2 and R3 are selected from octanoyl, nonanoyl, decanoyl and undecanoyl;
    R4 is H;
    l, m and n are 1; Y
    X1, X2, X3 and X4 are the same and are each methylene or a divalent radical of the formula:
    image2
    (IIa)
    (IIb)
    (IIc)
    (IId)
    (IIe)
    (IIf)
    [5]
    5. Resistive sensor (A) according to claim 4, wherein the divalent radical has the formula (IIc).
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    [6]
    6. Resistive sensor (A) according to claim 1, wherein said metal nanoparticles are of a metal selected from Au and Ag.
    [7]
    7. Resistive sensor (A) according to any of claims 1 or 6, wherein said metal nanoparticles have a particle size between 1 and 10 nm.
    [8]
    8. Device comprising the resistive sensor (A) according to any of claims 1 to 7.
    [9]
    Device according to claim 8, characterized in that it also comprises at least one resistive sensor (B) that includes a dielectric support (1) with electrodes (2) coated with carbon nanotubes (3) functionalized with carbonyl groups and carboxyl and decorated with metal nanoparticles (4), and does not include organic compound, where the sensor (B) does not react in the presence of benzene gas.
    [10]
    10. Device according to claim 9, wherein the resistive sensor (B) is also selective to nitrogen dioxide and / or ozone.
    [11]
    Device according to any one of claims 8 to 10, characterized in that said resistive sensor (A, B) also includes a microelectronic circuit for receiving and / or processing an electrical signal of the electrodes of said resistive sensor (A, B), and a transmitter to send the data obtained by said resistive sensor (A, B) to a remote receiver.
    [12]
    12. Use of the device according to any of claims 8 to 11 for the detection of benzene gas.
    [13]
    13. Method for obtaining a resistive sensor (A) according to any of claims 1 to 7, characterized in that it comprises the following steps:
    - select a dielectric support (1);
    - drawing on said support (1) a pair of electrodes (2) with the desired design;
    - treating the carbon nanotubes (3) with oxygen to give carbon nanotubes functionalized with carbonyl and / or carboxyl groups;
    - decorate the carbon nanotubes (3) with metal nanoparticles (4);
    - deposit the carbon nanotubes (3) on the electrodes (2) as a coating, where the carbon nanotubes (3) are interchangeably decorated with
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    nanoparticles (4) before or after depositing on the electrodes (2);
    - preparing a solution of an organic compound of the resorcin [4] arene group;
    - immerse the dielectric support (1) with electrodes (2) coated with carbon nanotubes (3) functionalized with carbonyl and carboxyl groups and decorated with metal nanoparticles (4) in the solution prepared to join the organic compound of the resorption group [4 ] sand to the metal nanoparticles (4) and form a monolayer (5) as a coating.
    [14]
    14. Method according to claim 13, wherein the dielectric support (2) is of a material selected from the group comprising a flexible polymer, a ceramic material, oxidized silicon or sapphire.
    [15]
    15. Method according to claim 13, wherein the electrodes (2) are drawn on the support (2) by screen printing, evaporation, cathode spraying or injection printing.
    [16]
    16. Method according to claim 13, wherein the carbon nanotubes (3) are treated with oxygen by radiofrequency cold plasma or by a wet chemical process.
    [17]
    17. Method according to claim 13, wherein the carbon nanotubes (3) are decorated with metal nanoparticles (4) by evaporation, cathode spray, chemical vapor deposition or a colloidal solution of said nanoparticles in a radiofrequency plasma.
    [18]
    18. Method according to claim 13, wherein the carbon nanotubes (3) are deposited on the electrodes (2) by electrodeposition, injection printing, drip coating, screen printing or airbrush.
    [19]
    19. Method according to claim 13, wherein the formation of the monolayer of the organic compound of the resorption group [4] arene is carried out by the self-assembled monolayer (SAM) technique for the appropriate time and temperature, followed by drying or evaporation of the solvent.
    [20]
    20. Method according to any of claims 13 to 19, wherein the following steps are carried out:
    - select a dielectric support (1) of alumina;
    - drawing on said support a pair of electrodes (2) of Pt with the desired design;
    - treat carbon nanotubes (3) multipared with oxygen by bombardment by a cold plasma of radio frequency of Ar;
    5 - deposit carbon nanotubes (3) multipared by airbrush over
    electrodes (2) as a coating and before decorating the nanotubes with the gold metal nanoparticles (4);
    - decorate the carbon nanotubes (3) multipared with metal nanoparticles (4) of gold by means of cathode spraying;
    10 - prepare a solution of an organic compound of the resorcin [4] arene group;
    - immersing in said solution the dielectric support with electrodes coated with carbon nanotubes (3) multipared functionalized with carbonyl and carboxyl groups and decorated with gold metal nanoparticles (4) to form a monolayer (5) as a coating of organic compound.
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    WO2016079356A1|2016-05-26|
    ES2574657B1|2017-04-19|
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    CN108802107B|2017-05-02|2021-02-09|中国石油化工股份有限公司|Method for measuring concentration of hydrogen sulfide based on resistance|
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