• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A sensor and a method of using the sensor are disclosed. The sensor includes a conductive region in electrical communication with two electrodes, the conductive region including single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex. The sensor can be used to detect volatile compounds that have a double or triple bond.
    公开号:EP3708572A1
    申请号:EP20162159.6
    申请日:2020-03-10
    公开日:2020-09-16
    发明作者:Alexander Wei；Lia Antoaneta Stanciu；Winston Yen-Yu Chen；Aiganym Yermembetova；Benjamin M. Washer
    申请人:Carrier Corp；
    IPC主号:C07F5-00
    专利说明:
    [0001] Exemplary embodiments pertain to the art of sensor compositions based on metal-ligand complexes.
    [0002] Volatile compounds with a double bond form an important group of compounds for detection. In particular, volatile alkenes, such as ethylene, are analytes of considerable importance. In particular, the detection of ethylene is important to industries related to produce and agriculture. Due to its small size and limited chemical functionality, however, ethylene is a challenging chemical analyte to detect. More efficient and sensitive methods of detection than those currently available are desired. BRIEF DESCRIPTION
    [0003] Disclosed is a sensor including a conductive region in electrical communication with two electrodes, the conductive region including single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex.
    [0004] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the nanosized particles of a metal dichalcogenide include MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, and combinations thereof.
    [0005] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes more than one mercaptoimidazolyl group.
    [0006] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes three mercaptoimidazolyl groups.
    [0007] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes a pyrazolyl or indolyl group in addition to the mercaptoimidazolyl group(s).
    [0008] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes Cu(I), Ag(I), or Au(I).
    [0009] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex is a complex of formula (II):
    [0010] Also disclosed is a method of sensing a volatile compound having a double or triple bond including exposing a sensor to a sample, the sensor including a conductive region in electrical communication with two electrodes, the conductive region including single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex, and measuring an electrical property at the electrodes.
    [0011] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the electrical property is conductivity.
    [0012] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the electrical property is resistivity.
    [0013] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the method further includes comparing an electrical property value obtained by measuring to a calibration curve to determine the quantity of a volatile compound having a double or triple bond present in the sample.
    [0014] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the volatile compound having a double or triple bond is ethylene.
    [0015] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the nanosized particles of a metal dichalcogenide include MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, and combinations thereof.
    [0016] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes more than one mercaptoimidazolyl group.
    [0017] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes three mercaptoimidazolyl groups.
    [0018] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes a pyrazolyl or indolyl group in addition to the mercaptoimidazolyl group(s).
    [0019] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex includes Cu(I), Ag(I), or Au(I).
    [0020] In addition to one or more of the features described above, or as an alternative to any of the foregoing embodiments, the mercaptoimidazolyl metal-ligand complex is a complex of formula (II):
    [0021] In another aspect, a method of preparing a sensor includes forming a conductive region including single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex, and placing the conductive region in electrical communication with two electrodes. BRIEF DESCRIPTION OF THE DRAWINGS
    [0022] The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:FIG. 1 is a graph of the electrode signal plotted against gas concentration. DETAILED DESCRIPTION
    [0023] A detailed description of one or more embodiments of the disclosed apparatus and method are presented herein by way of exemplification and not limitation with reference to the Figure.
    [0024] Volatile compounds with double or triple bonds are a group of important compounds for detecting and monitoring. The term volatile, as used herein, refers to compounds that are in the gas phase at standard temperature and pressure. Exemplary compounds include NO2, CO2, CO, and alkenes such as C2H4 (ethylene). As the hormone responsible for initiating the ripening of fruit as well as other processes in plant development, ethylene is an analyte of considerable importance to industries related to produce and agriculture. Due to its small size and limited chemical functionality, ethylene and other volatile alkenes are challenging chemicals to detect. Disclosed herein is a sensor and a method that is capable of detecting volatile compounds with double bonds such as ethylene and other volatile alkenes at levels down to 100 parts per billion (ppb).
    [0025] The sensor includes a conductive region in electrical communication with at least two electrodes. The conductive region includes single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex.
    [0026] Single-walled carbon nanotubes are known materials and are commercially available. Exemplary materials include single-walled nanotubes available from NanoIntegris, US Research Nanomaterials, Inc., Millipore Sigma (formerly Sigma Aldrich), and NanoLab, Inc.
    [0027] Metal dichalcogenides include transition metal dichalcogenides which are compounds formed from a Group 6B metal and a chalcogenide (S, Se, and Te). Exemplary metal dichalcogenides include MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, and combinations thereof. The metal dichalcogenide is in the form of nanosized particles. "Nanosized" as it applies to the metal dichalcogenides refers to the fact that the material has a thickness of less than or equal to 100 nanometers. The metal dichalcogenides are typically available in a flake form with a thickness of 100 nanometers or less although other physical forms are not excluded such as few-layer or single-layer materials, with the caveat that the physical form has at least one linear dimension that is less than or equal to 100 nanometers.
    [0028] The mercaptoimidazolyl metal-ligand complex is a multidentate coordination complex comprising one or more mercaptoimidazolyl groups. The arms of the multidentate ligand (groups on the boron atom) can be the same (homoleptic) or different (heteroleptic). For example, one arm can comprise a mercaptoimidazolyl group and a second arm can comprise a pyrazolyl or indolyl group. It is also contemplated that a multidentate ligand may comprise more than one mercaptoimidazolyl group or a combination of mercaptoimidazolyl group(s) and pyrazolyl group(s) or indolyl groups or both. The mercaptoimidazolyl metal-ligand complex may have formula (I)
    [0029] A more specific example of a mercaptoimidazolyl metal complex is shown in formula (II).
    [0030] The metal in the mercaptoimidazolyl metal complex may include Group 11 elements such as Cu(I), Ag(I), and Au(I).
    [0031] The single-walled carbon nanotubes and nanosized particles of a metal dichalcogenide are applied to a substrate. The substrate may be a flexible polymer film or other suitable material. Exemplary flexible polymer films include polyethylene terephthalate, polyethylene, polypropylene, polyamide, and polyvinyl chloride. The electrodes may be deposited on the substrate before the application of the single-walled carbon nanotubes and nanosized particles of metal chalcogenide. The single-walled carbon nanotubes and nanosized particles of a metal chalcogenide may be applied by spray deposition. An example of a formulation that has been used to prepare working sensors is provided as Table 1. These materials are either codeposited or sequentially deposited. After the single-walled carbon nanotubes and nanosized particles of a metal dichalcogenide are applied to the substrate the mercaptoimidazolyl metal-ligand complex is deposited on top of the single-walled carbon nanotubes and nanosized particles of a metal dichalcogenide. The mercaptoimidazolyl metal-ligand complex may be applied by drop casting, dip coating, spray coating, or by electrospray. The layered material is then dried and is ready for use. Table 1. H2O 91 wt% iPrOH 9 wt% MOS2 1.9 ppm SWCNT 2.5 ppm sodium deoxycholate (surfactant) < 1 wt%
    [0032] A method of sensing a volatile compound having a double or triple bond includes exposing a sensor as described above to a sample and measuring an electrical property at the electrodes. The electrical property can be conductivity or resistivity. The method can also include comparing the obtained electrical property value to a calibration curve to determine the quantity of the volatile compound present in the sample.
    [0033] FIG. 1 shows data obtained using nanosized particles of MoS2 in combination with single-walled carbon nanotubes as the underlayer. The underlayer was coated with mercaptoimidazolyl metal-ligand complex as shown in formula (II). The peaks are due to ethylene absorption (the samples used for ethylene exposure contained ethylene in amounts from 10 to 0.1 ppm).
    [0034] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, element components, and/or groups thereof.
    [0035] While the present disclosure has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present disclosure. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present disclosure without departing from the essential scope thereof. Therefore, it is intended that the present disclosure not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this present disclosure, but that the present disclosure will include all embodiments falling within the scope of the claims.
    权利要求:
    Claims (15)
    [0001] A sensor comprising a conductive region in electrical communication with two electrodes, the conductive region comprising single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex.
    [0002] The sensor of claim 1, wherein the nanosized particles of a metal dichalcogenide comprise MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, and combinations thereof.
    [0003] The sensor of claim 1 or 2, wherein the mercaptoimidazolyl metal-ligand complex comprises a homoleptic ligand with three mercaptoimidazolyl groups.
    [0004] The sensor of any one of claims 1 to 3, wherein the mercaptoimidazolyl metal-ligand complex comprises heteroleptic ligand with a pyrazolyl or indolyl group in addition to the mercaptoimidazolyl group.
    [0005] The sensor of any one of the preceding claims, wherein the mercaptoimidazolyl metal-ligand complex comprises Cu(I), Ag(I), or Au(I).
    [0006] The sensor of any one of the preceding claims, wherein the mercaptoimidazolyl metal-ligand complex is a homoleptic complex of formula (II):
    [0007] A method of sensing a volatile compound having a double or triple bond comprising exposing a sensor to a sample, the sensor comprising a conductive region in electrical communication with two electrodes, the conductive region including single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex, and measuring an electrical property at the electrodes.
    [0008] The method of claim 7, further comprising comparing an electrical property value obtained by measuring to a calibration curve to determine the quantity of a volatile compound having a double or triple bond present in the sample.
    [0009] The method of claim 8, wherein the volatile compound having a double or triple bond is ethylene.
    [0010] The method of any one of claims 7 to 9, wherein the nanosized particles of a metal dichalcogenide comprise MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, and combinations thereof.
    [0011] The method of any one of claims 7 to 10, wherein the mercaptoimidazolyl metal-ligand complex comprises three mercaptoimidazolyl groups.
    [0012] The method of any one of claims 7 to 11, wherein the mercaptoimidazolyl metal-ligand complex comprises a pyrazolyl or indolyl group in addition to the mercaptoimidazolyl group.
    [0013] The method of any one of claims 7 to 12, wherein the mercaptoimidazolyl metal-ligand complex comprises Cu(I), Ag(I), or Au(I).
    [0014] The method of claim 7, wherein the mercaptoimidazolyl metal-ligand complex is a complex of formula (II):
    [0015] A method of preparing a sensor comprising forming a conductive region including single-walled carbon nanotubes, nanosized particles of a metal dichalcogenide, and a mercaptoimidazolyl metal-ligand complex, and placing the conductive region in electrical communication with two electrodes.
    类似技术:
    公开号 | 公开日 | 专利标题
    Assen et al.2017|MOFs for the sensitive detection of ammonia: deployment of fcu-MOF thin films as effective chemical capacitive sensors
    Öztürk et al.2016|Electrochemically growth of Pd doped ZnO nanorods on QCM for room temperature VOC sensors
    Abd El-Lateef2015|Experimental and computational investigation on the corrosion inhibition characteristics of mild steel by some novel synthesized imines in hydrochloric acid solutions
    Pandeeswari et al.2014|High sensing response of β-Ga2O3 thin film towards ammonia vapours: influencing factors at room temperature
    Cuartero et al.2018|All-solid-state potentiometric sensors: A new wave for in situ aquatic research
    Ensafi et al.2013|Sensitive voltammetric determination of diclofenac using room-temperature ionic liquid-modified carbon nanotubes paste electrode
    Zhou et al.2003|Silicon nanowires as chemical sensors
    Ibañez et al.2012|Chemiresistive sensing with chemically modified metal and alloy nanoparticles
    Renedo et al.2007|Anodic stripping voltammetry of antimony using gold nanoparticle-modified carbon screen-printed electrodes
    Mubeen et al.2007|Palladium nanoparticles decorated single-walled carbon nanotube hydrogen sensor
    Abu-Shawish2009|A mercury | selective sensor based on N, N′-bis |-phenylenediamine as neutral carrier for potentiometric analysis in water samples
    Morrison1981|Semiconductor gas sensors
    Baghayeri et al.2020|Application of graphene/zinc-based metal-organic framework nanocomposite for electrochemical sensing of As | in water resources
    US20160011135A1|2016-01-14|Devices and methods for determination of species including chemical warfare agents
    Lewis2004|Comparisons between mammalian and artificial olfaction based on arrays of carbon black− polymer composite vapor detectors
    Rosolina et al.2015|Direct determination of cadmium and lead in pharmaceutical ingredients using anodic stripping voltammetry in aqueous and DMSO/water solutions
    Ndlovu et al.2014|Voltammetric detection of arsenic on a bismuth modified exfoliated graphite electrode
    Bakker et al.2000|Selectivity of potentiometric ion sensors
    Nagarajan et al.2017|Adsorption studies of alcohol molecules on monolayer MoS2 nanosheet—a first-principles insights
    Carrera et al.2017|Electrochemical determination of arsenic in natural waters using carbon fiber ultra-microelectrodes modified with gold nanoparticles
    Renedo et al.2007|A novel method for the anodic stripping voltammetry determination of Sb | using silver nanoparticle-modified screen-printed electrodes
    US8497130B2|2013-07-30|Method for determining the partition coefficient of an analyte
    Mubeen et al.2010|Sensitive detection of H2S using gold nanoparticle decorated single-walled carbon nanotubes
    Travlou et al.2015|Activated carbon-based gas sensors: effects of surface features on the sensing mechanism
    Clément et al.2015|Deep Cavitand Self‐Assembled on Au NPs‐MWCNT as Highly Sensitive Benzene Sensing Interface
    同族专利:
    公开号 | 公开日
    US20200291044A1|2020-09-17|
    SG10202002244UA|2020-10-29|
    CN111693575A|2020-09-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2020-08-14| STAA| Information on the status of an ep patent application or granted ep patent|Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
    2020-08-14| PUAI| Public reference made under article 153(3) epc to a published international application that has entered the european phase|Free format text: ORIGINAL CODE: 0009012 |
    2020-09-16| AX| Request for extension of the european patent|Extension state: BA ME |
    2020-09-16| AK| Designated contracting states|Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
    2021-03-19| STAA| Information on the status of an ep patent application or granted ep patent|Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
    2021-04-21| RBV| Designated contracting states (corrected)|Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
    2021-04-21| 17P| Request for examination filed|Effective date: 20210315 |
    2021-08-04| STAA| Information on the status of an ep patent application or granted ep patent|Free format text: STATUS: GRANT OF PATENT IS INTENDED |
    2021-08-04| GRAP| Despatch of communication of intention to grant a patent|Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
    2021-08-25| RIC1| Information provided on ipc code assigned before grant|Ipc: C07F 15/04 20060101AFI20210719BHEP Ipc: C08F 110/02 20060101ALI20210719BHEP Ipc: G01N 27/12 20060101ALI20210719BHEP Ipc: G01N 33/00 20060101ALI20210719BHEP Ipc: C07F5/02 20060101ALI20210719BHEP |
    2021-09-01| INTG| Intention to grant announced|Effective date: 20210805 |
    2021-10-09| GRAS| Grant fee paid|Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
    2021-10-15| STAA| Information on the status of an ep patent application or granted ep patent|Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
    2021-10-15| GRAA| (expected) grant|Free format text: ORIGINAL CODE: 0009210 |
    2021-11-17| AK| Designated contracting states|Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
    2021-11-17| REG| Reference to a national code|Ref country code: GB Ref legal event code: FG4D |
    2021-12-08| REG| Reference to a national code|Ref country code: IE Ref legal event code: FG4D |
    2021-12-09| REG| Reference to a national code|Ref country code: DE Ref legal event code: R096 Ref document number: 602020001002 Country of ref document: DE |
    2021-12-15| REG| Reference to a national code|Ref country code: AT Ref legal event code: REF Ref document number: 1447991 Country of ref document: AT Kind code of ref document: T Effective date: 20211215 |
    2022-01-19| REG| Reference to a national code|Ref country code: NL Ref legal event code: FP |
    优先权:
    申请号 | 申请日 | 专利标题
    [返回顶部]