WO2008151917A1 - Procédé de revêtement métallique d'un matériau d'échafaudage poreux - Google Patents

Procédé de revêtement métallique d'un matériau d'échafaudage poreux Download PDF

Info

Publication number
WO2008151917A1
WO2008151917A1 PCT/EP2008/056388 EP2008056388W WO2008151917A1 WO 2008151917 A1 WO2008151917 A1 WO 2008151917A1 EP 2008056388 W EP2008056388 W EP 2008056388W WO 2008151917 A1 WO2008151917 A1 WO 2008151917A1
Authority
WO
WIPO (PCT)
Prior art keywords
porous material
gold
paint
metal
heating
Prior art date
Application number
PCT/EP2008/056388
Other languages
English (en)
Inventor
Mirek Macka (Miroslav)
Brett Paull
Marco Grundmann
Zarah Walsh
Silvija Abele
Original Assignee
Dublin City University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dublin City University filed Critical Dublin City University
Publication of WO2008151917A1 publication Critical patent/WO2008151917A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/282—Porous sorbents
    • B01J20/283—Porous sorbents based on silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
    • B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C03C17/10—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals by deposition from the liquid phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/80—Aspects related to sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J2220/82—Shaped bodies, e.g. monoliths, plugs, tubes, continuous beds

Definitions

  • the present disclosure generally relates to the field of porous materials and more particularly to a method of coating porous material with noble metals.
  • the present disclosure relates to the field of continuous, macroporous rods, structurally similar to sponges, which are often referred to as monoliths.
  • These porous materials are rigid, highly porous and to a high degree regular in their structure/morphology which makes them suitable for use in science technology and engineering for a variety of purposes.
  • One such purpose relates to chemistry and involves a flow of fluid through the porous material for separation methods.
  • Monoliths for chromatographic purposes are generally silica or organic polymer based.
  • Noble metal sponge-like materials have been created for a wide variety of purposes. As these noble metals, such as gold, sponge-like materials have been created without any kind of underlying support/scaffold material, they can only yield mechanical strength and rigidity corresponding to the noble metal itself but not higher than that of the noble metal.
  • monolayers of noble metal nano-particles have been deposited in the internal channels of monolithic supports but they do not provide a continuous surface coverage and thus, do not have high surface conductivity.
  • a method for coating a porous material with a noble metal includes the steps of diluting noble-metal paint with a solvent, flushing a porous material with the noble -metal paint, drying the porous material in air flow and applying a high temperature treatment to the porous material.
  • the paint may be a gold paint that has a gold content of about 12%, however, it is contemplated according to the present disclosure that a wide variety of paints or coating materials can be used.
  • the solvent used may be a variety of solvents, however, in an exemplary embodiment trichloroethylene is used.
  • the high temperature treatment comprises the steps of allowing remaining solvent to evaporate at room temperature, heating the porous material up to higher than 700 0 C at rate from 5 to 20 °C/min, heating the porous material at desired maximum temperature for 10 to 30 minutes and cooling the porous material to room temperature at rate from about 5 to 20 °C/min.
  • FIG. 1 is an exploded view of a scanning electron microscope (SEM) image of an gold- coated silica monolith with a schematic showing a nano-layer coating of noble metal on the walls of a macropore in the monolithic scaffold in accordance with the present disclosure
  • FIG. 2 is a schematic of an untreated monolithic scaffold in accordance with the present disclosure
  • FIG. 3 is flow diagram of an exemplary embodiment in accordance with the present disclosure.
  • FIG. 4 is a plan view of a tubing system in accordance with the present disclosure
  • FIG. 5 is a graph of a heating profile of an exemplary embodiment in accordance with the present disclosure
  • FIG. 6(a) - FIG 6(e) are perspective views of pieces of a micro fluidic chip in accordance with the present disclosure
  • FIG. 7(a) and (b) are SEM images of coated and uncoated silica monoliths in accordance with the present disclosure
  • FIG. 8 are images from EDX analysis on a monolith treated in accordance with the present disclosure
  • FIG. 9(a) and FIG 9(b) depict mechanical profiles of slides coated with undiluted and diluted paint in accordance with the present disclosure
  • FIG. 10 is a graph of the thickness of gold layer versus gold paint dilution in accordance with the present disclosure
  • FIG. 1 l(a) and FIG. 1 l(b) depict a gold coated glass slide before and after treatment with THF in accordance with the present disclosure
  • FIG. 12 is a perspective view of a microfluidic chip with encased gold-coated monoliths in accordance with the present disclosure.
  • FIG. 13 is a perspective view of a set up for testing back-pressure in accordance with the present disclosure.
  • the present disclosure provides a process for producing nano-layers of metals, e.g., noble metals such as gold, on underlying macroporous monolithic scaffolds by treating their surface with a commercial liquid noble metal formulation normally used for painting glass and porcelain.
  • metals e.g., noble metals such as gold
  • the noble metal formulation can be suitably diluted with a desired solvent to produce, after drying in a controlled atmosphere, a homogeneous coating. This step can then be followed by subsequent programmed-temperature treatment in a furnace, to produce a nano-layer of noble metal of desired thickness.
  • the method according to the present disclosure has a variety of applications.
  • One application is the selective preconcentration of amino acids, peptides, proteins and other thiol group containing analytes on gold coated monoliths.
  • Another application is utilizing the wealth of thiol-based chemistry, adsorption of thiol-based ligands onto gold coated monolithic scaffolds, thus introducing potential for target analyte-specific analyses.
  • the method may be used for utilizing the surface of a noble metal for a variety of electrochemical applications including creating active chromatographic stationary phases, the surface properties of which would be switchable upon application of external potential (voltage) and allowing electrochemical reactions on the surface upon applying an external potential.
  • Another electrochemical application includes utilizing the porous noble metal structures as porous flow- through electrodes e.g., for (i) electrochemical detection in flowing systems (flow-injection analysis, liquid chromatography etc.) and (ii) preconcentration of metal ions from mostly but not exclusively aqueous samples using the principle of "stripping voltammetry" with the noble metal coated monolith as a replacement for the classical hanging mercury drop electrode.
  • the porous monolithic scaffold can be any porous material capable of withstanding high temperatures necessary for the high temperature treatment of the metal paint further described below.
  • the porous scaffold material can be, for example, a silica monolith used for chromatography.
  • the coating formulation may be a variety of materials in accordance with the present disclosure.
  • the coating formulation in an exemplary embodiment is a liquid metal paint.
  • the liquid metal paint can be any formulation containing a metal in the form of a liquid paint that produces a layer of the metal after high temperature treatment.
  • One example, as used in an exemplary embodiment, is commercial gold paint used to paint glass and porcelain.
  • the coating thickness is governed by diluting the liquid noble metal formulation in a certain ratio with a desired solvent and can be adjusted and determined before application to the silica monolith.
  • the surface coating may be further analyzed by scanning electron microscopy (SEM), energy-dispersive X-ray microanalysis (EDX) and optical microscopy as further described below.
  • Figure 1 shows an exploded view of the noble-metal nano-layer coated monolithic scaffold 10 according to the present disclosure.
  • the macropore of a monolithic scaffold 12 is generally silica based but can be based on any material which can withstand the high temperatures of the heat treatment, which is applied to the paint in the final stages of the process.
  • the walls of macropore 12 can be coated with a nano-layer of noble-metal 14 according to the present disclosure.
  • the noble metal nano-layer coated monolith scaffold can be prepared following the treatment procedure as described in the present disclosure. Procedure
  • the gold paint having a 12 % gold content was used to form a nano-layer on a monolith scaffold.
  • Other paints may be used in accordance with the present disclosure.
  • platinum, palladium and titanium oxide paints can be used.
  • the method according to the present disclosure may be used to prepare a variety of coated monolithic scaffolds.
  • a silica monolith as depicted in Figure 2 was used.
  • Figure 2 depicts a filled capillary 16 containing the porous monolithic silica scaffold 18, a fused silica layer 20 and a layer of polyimide coating 22.
  • a commercial silica-Cis monolithic column for nano-LC in a 100 micrometres ID fused silica capillary can be used, such as Caprod provided by Merck or Onyx provided by Phenomenex.
  • the process for preparing the coated monolithic scaffold is shown in Figure 3.
  • the gold paint is diluted using trichloro ethylene at a volume ratio 1:10 shown at step 24, is generally a sufficient dilution, however, the thickness of the gold layer can be modified by increasing or decreasing the quantity of solvent. The relationship between thickness and quantity of solvent is approximately inversely proportional.
  • the monolithic porous silica capillary is flushed with the diluted gold paint formulation using for example, a peristaltic pump.
  • FIG. 4 An exemplary tubing system for flushing paint through the silica monoliths is depicted at Figure 4.
  • the capillary 34 is connected via finger tight fitting-union-ferrule 36 to a piece of polytetrafluoroethylene (PTFE) tubing 38 containing the diluted gold paint.
  • Tubing 36 is connected via a further ferrule -union- ferrule connection 40 to a peristaltic tubing 42.
  • a peristaltic pump methanol is pumped through the peristaltic tubing 42 to drive the gold paint into the capillary 34.
  • the capillary is then dried in air flow at step 28 by, for example, using the same peristaltic pump allowing air flow through.
  • a flow of air after the process of filling of the capillaries is desirable to (1) expel excess amounts of the liquid gold formulation in order to prevent a blockage of and achieve an even surface coating of the monoliths' macropores, and (2) evaporate the gold paint's solvent quickly at room temperature to avoid uneven structures. Airflow is allowed to continue until no further liquid flow from the capillary is observed. Following the evaporation of most of the trichloroethylene, air is allowed to flow through the capillaries for about an additional five minutes.
  • high temperature treatment at approximately 750 0 C is applied to the capillary using a tube furnace at step 30. It is envisioned that the high temperature treatment can be applied using a variety of suitable equipment for drying at the desired temperatures in accordance with the present disclosure.
  • the heating starts at room temperature to allow any remaining solvent to evaporate.
  • heating of 5 ° C/min up to 750 0 C is applied to the capillary. This heating can be done in a range of approximately 5-20 °C/min up to the desired temperature.
  • the capillary is then treated for 20 minutes at 750 0 C. This treating period may also be modified based on the rate of heating and cooling.
  • the capillary is cooled with the speed of 20 °C/min down to room temperature.
  • the cooling rate can be in the range of about 5-20 °C/min.
  • the end temperature is room temperature, which is approximately 24 0 C.
  • This heating profile is depicted in Figure 5.
  • a variety of heating profiles can be implemented according to the present disclosure to achieve the desired coated monolithic scaffold. As a result pink/red color monolith was obtained in the capillary which shows the results of gold coating onto the monolith's surface.
  • the gold coated monolith is encased in a micro-milled poly methyl methacrylate (PMMA) chip as illustrated in Figure 6 because removal of the protective polyimide coating around the capillary during heat treatment (polyimide decomposes at approx. 350 0 C) renders the capillary extremely fragile.
  • PMMA poly methyl methacrylate
  • the coated monolithic scaffold may be incorporated into a variety of chip formats or other rigid molds as long as there is a rigid outer shell to protect the uncoated capillary within.
  • the monolithic scaffold may also be encased in polyetheretherketone (PEEK) tubing and plumbed directly into a high performance liquid chromatography (HPLC) instrument and detector for carrying out chromatographic separations.
  • PEEK polyetheretherketone
  • HPLC high performance liquid chromatography
  • the thermally treated capillaries are placed into channels 32 and the parts depicted in 6(b), 6(c) and 6(d) are bonded together.
  • Figure 6(e) depicts a micro-fluidic chip with channels 36 and one capillary 38.
  • Figure 7 (a) is an SEM image of a coated silica monolith
  • Figure 7(b) is a SEM image of an uncoated monolith.
  • EDX microanalysis was also performed at 2OkV, mag. 800x and working distance (WD) 15mm.
  • the EDX results show that after high temperature treatment of gold-treated silica monoliths, there were only oxygen, silica and gold present thus, showing that the method according to the present disclosure is appropriate for coating gold onto silica monoliths.
  • the EDX analysis images and screenshot are depicted in Figure 8.
  • Figure 9(a) and 9(b) Mechanical profilometry was performed to measure the thickness of the gold layer formed after thermal treatment and the results are shown in Figure 9(a) and 9(b) .
  • Figure 9(a) shows the mechanical profile for a gold layer coated silica slide where the gold was undiluted. This produced about a 1 micrometer thick gold layer.
  • Figure 9(b) depicts the mechanical profile for a gold layer coated silica slide. This gold layer was produced from gold paint diluted at a 1 :10 ratio, which produced a gold layer having a thickness of approximately 15 nano-meters. This was performed as an indirect method to estimate the thickness of the gold nano-layer in the internal channels of the monolith.
  • Silica slides were used as a substitute for the monolith, these were coated with diluted gold paint (various dilutions), air dried and then thermally treated under the same conditions as the gold coated monoliths, following the heating profile as shown in Figure 5. Results showing thickness of the layer versus dilution of the paint are shown in Figure 10. Ten times diluted paint resulted in a gold nano-layer of about 15 nanometers. The results showed the macropores of the monolith are not filled and the nano-layer covers the inner walls of the pores. Thus, the basic monolithic scaffold retains the same structure as it had prior to the coating process, as previously discussed with respect to Figure 7.
  • the chemical stability of the gold nano-layer was also tested in common organic solvents.
  • Gold-coated and thermally treated glass slides were immersed in the following solvents: trichloroethylene (TCE) - solvent used to make gold paint dilutions; tetrahydrofuran (THF) - strong solvent, which can even dissolve some polymer materials; and acetonitrile (ACN) - a commonly used eluent in separations science.
  • TCE trichloroethylene
  • THF tetrahydrofuran
  • ACN acetonitrile
  • Figure 11 (a) illustrates a gold nano- layer coated glass slide before treatment with THF
  • Figure 11 (b) illustrates the glass slide after 8 minutes of treatment with THF.
  • the structure of the coated glass slide after soaking in TCE, THF and ACN for more than 2 days was also observed.
  • Five percent nitric acid solution which is a strong oxidising agent and so could dissolve the gold-layer, does not affect the gold layer after 4 h of treatment.
  • microfluidic chip with encased capillaries, sputtered electrodes and encased tubings was used for backpressure measurements and chromatographic analysis.
  • the microfluidic chip is depicted in Figure 12.
  • the microfluidic chip 40 holds the encased capillaries 42 to be tested.
  • a High Performance Liquid Chromatography pump 44 is connected to PEEK tubing (ID 100 micrometres) 46 by a ferrule 56.
  • the PEEK tubing 46 is connected to a ferrule -union-ferrule fitting 52 attached to the outlet tubing on a micro-fiuidic chip 48.
  • Eluent is pumped from a reservoir of eluent 50 through PTFE tubing 54 by the HPLC pump 44 into the chip 48.
  • the pump has an integrated pressure gauge which records the change in flow resistance (back- pressure) as the flow rate changes. Increasing the flow step-wise and recording the backpressure change with each increase allows a graph to be plotted of flow rate vs. backpressure.
  • This method is a good method of estimating the flow properties of the monolith and in this case whether the coating has changed the porosity of the monolithic scaffold.
  • This analysis was performed to determine if the macropores of the monolithic scaffold were open enough to let eluent through.
  • Factory analysis as stated in the literature showed that backpressure using 70% ACN in water as an eluent on unmodified capillary is about 0.4 bar per 1 mm (at flow-rate 4 ⁇ L per minute).
  • Gold coated capillary according to the present disclosure showed a backpressure of 0.31 bar per 1 mm, using water as an eluent at flow rates up to 5 ⁇ L per minute.
  • the results were slightly different from literature value, however, the results showed that the pores are sufficiently open to allow eluent flow through the pores of the gold coated monolith scaffold prepared in accordance with the present disclosure.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Micromachines (AREA)

Abstract

L'invention propose un procédé pour revêtir un matériau poreux. Le procédé consiste à diluer une peinture à métal noble par un solvant, à rincer un matériau poreux à l'aide de la peinture à métal noble, à sécher le matériau poreux dans un écoulement d'air et à appliquer un traitement haute température au matériau poreux. Le traitement haute température peut comprendre les étapes consistant à amener le solvant restant à s'évaporer à température ambiante, à chauffer le matériau poreux jusqu'à plus de 700°C à raison de 5 à 20°C/min, à chauffer le matériau poreux à une température maximale désirée pendant 10 à 30 minutes et à refroidir le matériau poreux à température ambiante à raison d'environ 5 à 20°C/min.
PCT/EP2008/056388 2007-06-14 2008-05-23 Procédé de revêtement métallique d'un matériau d'échafaudage poreux WO2008151917A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US94389607P 2007-06-14 2007-06-14
US60/943,896 2007-06-14

Publications (1)

Publication Number Publication Date
WO2008151917A1 true WO2008151917A1 (fr) 2008-12-18

Family

ID=39780319

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/056388 WO2008151917A1 (fr) 2007-06-14 2008-05-23 Procédé de revêtement métallique d'un matériau d'échafaudage poreux

Country Status (1)

Country Link
WO (1) WO2008151917A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3340085A (en) * 1962-10-23 1967-09-05 Perkin Elmer Corp Gas chromatographic separating material
EP0668265A1 (fr) * 1994-02-21 1995-08-23 Cerdec Aktiengesellschaft Keramische Farben Dithiolates de monometal noble et leur utilisation pour la préparation des décorations contenant des métaux nobles sur des substrats aptes à la cuisson
US6136389A (en) * 1997-12-19 2000-10-24 Amt Holdings, Inc. Preparation of metal coatings
EP1369174A1 (fr) * 2002-06-03 2003-12-10 Shinwa Chemical Industries, Ltd. Support pour chromatographie, support pour prétraitement et kit pour sa préparation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3340085A (en) * 1962-10-23 1967-09-05 Perkin Elmer Corp Gas chromatographic separating material
EP0668265A1 (fr) * 1994-02-21 1995-08-23 Cerdec Aktiengesellschaft Keramische Farben Dithiolates de monometal noble et leur utilisation pour la préparation des décorations contenant des métaux nobles sur des substrats aptes à la cuisson
US6136389A (en) * 1997-12-19 2000-10-24 Amt Holdings, Inc. Preparation of metal coatings
EP1369174A1 (fr) * 2002-06-03 2003-12-10 Shinwa Chemical Industries, Ltd. Support pour chromatographie, support pour prétraitement et kit pour sa préparation

Similar Documents

Publication Publication Date Title
Herzog Recent developments in electrochemistry at the interface between two immiscible electrolyte solutions for ion sensing
US8602644B2 (en) Multifunctional micropipette biological sensor
Dietz et al. Recent developments in solid-phase microextraction coatings and related techniques
Economou et al. Mercury film electrodes: developments, trends and potentialities for electroanalysis
Bae et al. Electrochemistry at nanoporous interfaces: new opportunity for electrocatalysis
US5514253A (en) Method of measuring gas concentrations and microfabricated sensing device for practicing same
Baś et al. The renewable bismuth bulk annular band working electrode: Fabrication and application in the adsorptive stripping voltammetric determination of nickel (II) and cobalt (II)
JP4681052B2 (ja) フローセルおよびその製造方法
Budziak et al. Preparation and characterization of new solid-phase microextraction fibers obtained by sol–gel technology and zirconium oxide electrodeposited on NiTi alloy
Zhang et al. Growth of cedar-like Au nanoparticles coating on an etched stainless steel wire and its application for selective solid-phase microextraction
Ghalkhani et al. Electrochemical sensor based on multi-walled carbon nanotubes–boehmite nanoparticle composite modified electrode
US20110132196A1 (en) Gas chromatograph column and fabricating method thereof
Tian et al. In-situ hydrothermal synthesis of titanium dioxide nanorods on titanium wire for solid-phase microextraction of polycyclic aromatic hydrocarbons
Bertsch et al. Preparation of high resolution nickel open tubular columns
EP2534727A1 (fr) Cellule de détection électrochimique pour un système de chromatographie en phase liquide
Zhang et al. Rapid solid-phase microextraction of polycyclic aromatic hydrocarbons in water samples by a coated through-pore sintered titanium disk
Cortés-Salazar et al. Fountain pen for scanning electrochemical microscopy
JP2005031050A (ja) 重金属分析用マイクロリアクター
Golshadi et al. Template-based synthesis of aligned carbon nanotube arrays for microfluidic and nanofluidic applications
WO2008151917A1 (fr) Procédé de revêtement métallique d'un matériau d'échafaudage poreux
Shankaran et al. Determination of sulfur dioxide based on a silver dispersed functional self-assembled electrochemical sensor
CN103691487A (zh) 纳米Pd/Fe催化剂及其应用
Pacheco-Fernández et al. Metallic coatings in solid-phase microextraction: environmental applications
Xu et al. Development of novel solid-phase microextraction fibers
de Oliveira et al. Niobium (V) oxide coated on thin glass–ceramic rod as a solid phase microextraction fiber

Legal Events

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

Ref document number: 08759988

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08759988

Country of ref document: EP

Kind code of ref document: A1