WO2016045665A2 - Procédé et dispositif de synthèse électrochimique - Google Patents

Procédé et dispositif de synthèse électrochimique Download PDF

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Publication number
WO2016045665A2
WO2016045665A2 PCT/DE2015/100403 DE2015100403W WO2016045665A2 WO 2016045665 A2 WO2016045665 A2 WO 2016045665A2 DE 2015100403 W DE2015100403 W DE 2015100403W WO 2016045665 A2 WO2016045665 A2 WO 2016045665A2
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WO
WIPO (PCT)
Prior art keywords
working electrode
electrode
spiral
working
product
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PCT/DE2015/100403
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German (de)
English (en)
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WO2016045665A3 (fr
Inventor
Gerd-Uwe Flechsig
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Universität Rostock
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Application filed by Universität Rostock filed Critical Universität Rostock
Priority to EP15797246.4A priority Critical patent/EP3198060B1/fr
Priority to US15/514,233 priority patent/US20170335474A1/en
Publication of WO2016045665A2 publication Critical patent/WO2016045665A2/fr
Publication of WO2016045665A3 publication Critical patent/WO2016045665A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds

Definitions

  • the present invention relates to a process for the preparation of at least one product by electrochemical synthesis at a directly electrically heated working electrode (1), wherein at least one educt at the heated working electrode (1) reacts to the at least one product, or the use of a direct electrical heated working electrode (1) for the electrochemical synthesis of at least one product.
  • the invention also relates to a working electrode (1) designed especially for electrochemical synthesis, in particular in the form of a three-dimensional, preferably conical spiral.
  • the invention also relates to the synthesis / regeneration of an enyzmatic cofactor on a working electrode (1) according to the invention.
  • the working electrode may be constructed of a plurality of concentrically or parallel layers which are galvanically separated from one another, the outermost layer serving as an electrode and an inner layer as the heating element.
  • Indirect heating by means of galvanically separated from the electrode heaters is disadvantageous because the structure of the sensors is more complicated, the temperature changes due to the thermal inertia (due to the heat capacity) of the different layers usually slower and the possibilities of miniaturization are limited.
  • a direct electrical heating of the working electrode and simultaneously trouble-free electrochemical measurement can be made possible in the prior art by a so-called symmetrical arrangement or special filter circuits.
  • a variant of the directly heated working electrode has a third contact for the connection to the electrochemical measuring device exactly in the middle between the two contacts for the supply of the heating current. By this arrangement disturbing influences of the heating current are suppressed to the measurement signals.
  • the disadvantage here is especially the complex structure with three contacts per working electrode, the thermal disturbance by the heat dissipating third contact and the complicated miniaturization.
  • a symmetrical contacting takes place by means of a bridge circuit which enables direct heating (Wachholz et al., 2007, Electroanalysis 19, 535-540, in particular Fig. 3, Dissertation Wachholz 2009).
  • the working electrode can be designed so that the temperature distribution at the surface of the working electrode is uniform (DE 10 2004 017 750).
  • DE 10 2006 006 347 discloses advantageous directly electrically heatable electrodes.
  • microelectrodes heated in the prior art In order to carry out electrochemical analyzes in the trace range, it is therefore possible to use microelectrodes heated in the prior art.
  • the working electrode must be small in order to keep the metabolic rate negligibly small, thus avoiding changes in the analytical solution, which is a prerequisite in analytical voltammetry and amperometry, and also to keep the working range of the potentiostat galvanostat.
  • electrochemical cells In order to perform electrochemical syntheses at elevated temperatures, usually electrochemical cells are used, which are brought by a thermostat with water as the heat transfer medium to the desired temperature. The entire amount of electrolyte is heated with it.
  • the working electrode used here is generally a platinum mesh electrode, as a cylinder of 3 cm in diameter and 5 cm in length.
  • the expert in electrochemical syntheses has the problem that first of all a large amount of energy is needed to heat the entire solution, secondly that the temperature changes are very slow and thirdly sensitive substances in the electrolyte solution can be affected.
  • the object of the invention is therefore to provide an apparatus and a method to enable a high-mass electrochemical synthesis which reduces or at least partially overcomes the problems mentioned.
  • An object of the invention is a process for the preparation of at least one product by electrochemical synthesis at a directly electrically heated working electrode (1), in which at least one reactant reacts at the heated working electrode (1) to the at least one product.
  • a directly electrically heated working electrode (1) for the electrochemical synthesis of at least one product in which at least one educt reacts at the heated working electrode (1) to the at least one product.
  • the working electrode (1) can be directly heated by means of a symmetrical arrangement by means of a heating current designed as an alternating current, wherein the use of a bridge circuit, as explained above, is particularly advantageous.
  • the symmetrical contacting and direct heating of the working electrode (1) can thus be effected by a bridge circuit, for example, in Wachholz et al., 2007, Electroanalysis 19, 535-540, in particular FIG. 3.
  • the working electrode (1) can have a first and a second connection for the supply of the heating current, wherein the working electrode (1) is connected to a potentiostat via a third connection, wherein the connection of the third connection to the working electrode (1) via a Bridge circuit (2) which is connected to the first and second terminals is formed.
  • Suitable circuits are disclosed, for example, in DE 2006 006 347.
  • a heating current embodied as an alternating current can be used, in particular with a frequency of at least 1 kHz, preferably at least 20 kHz, more preferably at least 50 kHz or at least 100 kHz.
  • the electrochemically active surface of the working electrode (1) preferably comprises at least 1 ⁇ 10 6 m 2 , applicable for example for microscale synthesis, preferably 1 ⁇ 10 5 m 2 approximately on a half-scale or 1 ⁇ 10 4 m 2 on a larger laboratory scale to the area of one or more square meters are possible.
  • volume elements of the electrolyte solution are only heated very briefly when they come into contact with the working electrode (1), wherein the reactants are reacted electrochemically at the desired elevated temperature. Even unwanted secondary reactions at high temperature can be so minimized by the rapid cooling of each volume element as a result of thermal convection. It is achieved that selectively only the electrochemical reaction proceeds at elevated temperature.
  • cf. Arc combustion in the Birkeland-Eyde process (1904, US 775123) which takes into account similar considerations.
  • a process according to the invention can advantageously be used for various electrochemical syntheses, for example for oxidation, reduction, substitution, dehydrogenation, addition, cleavage, cyclization, dimerization, polymerization, protonation, deprotonation or elimination.
  • the at least one product of the reaction may be, for example, a nitrosogroup protein, gluconic acid, sorbitol, D-arabinose, adiponitrile, a regenerated cofactor such as NAD + or NADP + . It is particularly advantageous to carry out the process according to the invention if the product of the synthesis is a product which is unstable at the reaction temperature at the working electrode (1), since in this case the product is exposed to this temperature only for a minimal time.
  • Unstable means in this context that the stability at the reaction temperature is lower than the stability at a lower temperature (eg room temperature or 4 ° C), in particular at a triple or ten times lower stability based on the difference in the reaction rate.
  • the stability can be analyzed eg as a half-life. It is possible to cool the electrolyte solution, if it promotes the stability of starting material or product or the course of the reaction.
  • the indefinite article “a / a” always includes “two / more”, unless this is clearly to be understood differently from the context.
  • electrochemical synthesis it is of course also possible, e.g. a reaction of two reactants to one or two product (s) or from one reactant to one two products are carried out.
  • the reaction of the at least one starting material to the at least one product can also be catalyzed enzymatically, wherein optionally the enzyme and / or an optionally necessary cofactor is immobilized on the heated working electrode (1).
  • starting material (s), enzyme and / or cofactor can also be homogeneously distributed in the electrolyte solution.
  • a synthesis reaction of at least one product catalyzed by an enzyme requiring a cofactor such as NAD + or NADP + takes place.
  • the regeneration of the cofactor necessary for a continuation of the reaction takes place at the working electrode.
  • the synthesis of a product which is unstable at the reaction temperature is also conceivable in enzymatic catalysis.
  • the temperature of the working electrode can be pulsed for up to 300 ms, for example about 5-250 ms, 50-200 ms or 100-150 ms, but preferably shorter than 100 ms, be increased above the boiling point of the electrolyte surrounding the electrode.
  • This has the advantage of getting only a small part of the solution for a short time Period is heated. The short thermal convection occurring after the heat pulse makes stirring the solution unnecessary.
  • the short period of heating is positive for the stability of starting materials and products and possibly of enzymes that catalyze the reaction. For unstable educts or products, this advantage plays a special role. Furthermore, any deposits on the working electrode are removed so that it cleans itself.
  • the method according to the invention makes it possible to follow the substance conversion of the reaction coulometrically.
  • coulometric observation of the faradaic conversion of a synthesis reaction by measurement of the electrolytic current strength and calculation of the amount of charge / amount of substance as integral of the current over time is possible.
  • An object of the invention is also a device comprising two insulated conductors (3) which are interconnected by a thinner working electrode (1) in relation to the conductors, the working electrode (1) being an anode made of an electrode material such as a wire from precious metal, in particular gold or platinum, or from a carbon pin, eg Graphite, boron-doped diamond or glassy carbon, or of optically transparent conductive material such as ITO (indium-doped tin oxide) (an electrode material), preferably gold or platinum, wherein the working electrode (1) is preferably in the form of a spiral, preferably a three-dimensional spiral.
  • the cathode less noble metals such as copper, stainless steel or nickel can be used as electrode materials in addition to the materials mentioned.
  • the insulated conductors (3) may e.g. Copper pins or other good electrical conductors, e.g. are insulated by a glass tube or by a plastic coating, as well known in the art.
  • the spiral is configured as a conical spiral, in particular a conical spiral Archimedean spiral or an Archimedean sphere spiral or a Loxodrom.
  • a section of such a spiral is sufficient, in particular in the case of spherical spirals, it is even preferred that only a section increasing or decreasing in diameter (ie not first increasing and then decreasing) is used. Even irregular spiral shapes are possible.
  • a particularly advantageous embodiment is shown in FIG.
  • a sufficient distance between sections of the working electrode (1) should be ensured to prevent short circuits. It is useful to have a distance of about 1 to about 20 mm, preferably about 5 to about 15 mm or about 8 to about 10 mm. The distance is preferably uniform within the spiral.
  • the electrical contact points between working electrode (1) and insulated conductors (3) may be located approximately in the middle, that is on or near the central axis of the spiral. In this case, lower and upper contact point (5, 6) are preferably laterally slightly offset from each other. The contact point, which is connected to the outer, from the axis farthest side of the spiral, can also be guided along the outside of the spiral.
  • the three-dimensional spiral working electrode is oriented in relation to the insulated conductors and possibly the further structure of the device so that the diameter of the spiral decreases from bottom to top.
  • Preferred three-dimensional spiral shapes when the spiral working electrode is vertically aligned along its central axis, cause the working electrode to barely or preferably not vertically overlap when using the electrochemical synthesis device, ie, not heated to above the heated electrode by the heating of the working electrode Sections of the working electrode hits and these additionally heated. This ensures a uniform temperature of the working electrode, which is important for the synthesis process.
  • a further device comprising two insulated conductors (3), which are interconnected by a plurality of thinner working electrodes (1) in relation to the insulated conductors, the working electrodes (1) functioning as an anode a wire made of precious metal, in particular gold or platinum or else a pin of carbon, eg graphite, boron-doped diamond or glassy carbon, or of optically transparent conductive material, such as ITO (indium-doped tin oxide) (an electrode material).
  • ITO indium-doped tin oxide
  • the working electrodes (1) are designed so that no vertical superimposition of the working electrodes (1) takes place and this
  • (B) preferably from a lower contact point (5) with one of the insulated conductors (3) to a vertically and optionally horizontally offset upper contact point (6) with the other insulated conductor (3) extend, wherein the working electrodes (1) in a lower portion extending outwardly from the lower contact point (5), inclined upward in a central portion and inward in an upper portion toward the upper contact point (6), the inclination in the central portion being such that no vertical Overlaying the sections of the working electrodes (1) or the working electrodes (1) takes place.
  • the working electrode has essentially a stile-like shape, as in a wall bar, the spars of which form the insulated conductors (3), and which is obliquely positioned to prevent a vertical superposition of the working electrodes (rungs). It can be e.g. to act parallel glass or graphite pencils, which are ladder-like, but arranged obliquely. These parallel pins are connected by insulated conductors, resulting in a lattice-shaped working electrode.
  • the pins may e.g. be attached to an insulating grid or cage. This may be a stretched, e.g. plane or e.g. cylindrical shape.
  • screen printing electrodes e.g. made of glassy carbon in parallel form is possible.
  • the insulating support (7) may e.g. be a cage or a grid.
  • a free circulation of the electrolyte by the carrier (7) is not severely restricted.
  • the insulating support is preferably made of or comprises an insulating material, the material being glass, ceramic or plastic, e.g. Polytetrafluoroethylene (PTFE, Teflon®), can be. If sufficient stability is ensured by the material and the shape of the electrode (1), the use of a carrier is not necessary.
  • the working electrode (1) a surface area of at least lxlO "6 m 2, preferably lxl 0" 5 m 2 or lxl 0 "4 m 2.
  • the diameter may for example, about 0.05-5 mm, preferably 0, 1-
  • the length may be for example 2.5-100 cm, preferably 5-50 cm, 10-40 cm, 15-30 cm or 20-25 cm The length depends on the cross-sectional area and the resistivity of the
  • the resistance between the two heating current contacts (5) and (6) should be, for example, about 0.5 to 20 ohms, preferably 1 to 10 ohms, so that on the one hand the voltage drop between the contacts will not too large, on the other hand, the resistance is still easily measured by electronics and thus the heating power automatically adjustable (Flechsig, Gründler, Wang, 2004, EP 1743173, DE 10 2004 017 750 B4).
  • the electrode length would have to be 14.4 m, resulting in an electrode surface of 446 cm 2 . That would be pilot scale.
  • the working electrode (1) can be directly heated by means of a symmetrical arrangement by means of a heating current designed as an alternating current.
  • the symmetrical contacting preferably takes place via a bridge circuit (2), as explained above.
  • a symmetrically designed inductance is provided (7).
  • the working electrode (1) can be provided with a galvanostat or a potentiostat, a reference electrode (REF) and a counterelectrode (AUX), which appears either as an anode or a cathode, depending on whether at the working electrode a reduction or an oxidation expires, be connected or connected to it.
  • This galvanostat or potentiostat can also be a simpler power supply unit with a bipolar output, on whose displays only the decomposition voltage between working and counter electrode, as well as the electrolysis current are displayed.
  • the counterelectrode is preferably arranged at a distance of at least 1 mm, preferably at least 5 mm, from the working electrode so that the thermal convection around and above the working electrode does not lead to mixing of the space around the counterelectrode it is below when used. This avoids that the reverse reaction of the product takes place to the educt at the counter electrode. It also prevents unwanted Move products from the counter electrode to the working electrode. Examples include, in particular, the halogens chlorine and bromine, but also oxygen and others. For example, it may be desirable to conduct cathodic reduction at a strongly negative potential in a chloride-containing solution.
  • a cooler e.g. Arrange a cooling Peltier element on the bottom of the cell.
  • the device may comprise the components shown in FIG. 2 of the present application. It can also comprise the components shown in DE 10 2006 006 347, Fig. 1, Fig. 2, Fig. 3 or Fig. 4 (preferably Fig. 1) in a corresponding arrangement.
  • the reaction takes place at the directly heated working electrode of a device according to the invention, in particular a device which comprises two insulated conductors (3) which are interconnected via a thinner working electrode (1) in relation to the conductors are, wherein the working electrode (1) made of a wire of an electrode material such as gold, platinum and carbon (eg graphite, boron-doped diamond or glassy carbon) or ITO (as anode or cathode) or less noble metals such as copper, stainless steel or nickel (as Cathode), wherein the working electrode (1) has the shape of a spiral, preferably a three-dimensional spiral having.
  • an electrode material such as gold, platinum and carbon (eg graphite, boron-doped diamond or glassy carbon) or ITO (as anode or cathode) or less noble metals such as copper, stainless steel or nickel (as Cathode)
  • the working electrode (1) has the shape of a spiral, preferably a three-dimensional spiral having.
  • the invention also relates in particular to a process for the synthesis or regeneration of a cofactor of an enzymatic reaction in which the synthesis or regeneration takes place at a directly electrically heatable working electrode, preferably at the directly heated working electrode of a device according to the invention.
  • the working electrode (1) being made of a wire of an electrode material such as gold, Platinum and carbon (eg graphite, boron-doped diamond or glassy carbon) or ITO (as Anode or cathode) or less noble metals such as copper, stainless steel or nickel (as a cathode), wherein the working electrode (1) has the shape of a spiral, preferably a three-dimensional spiral.
  • an electrode material such as gold, Platinum and carbon (eg graphite, boron-doped diamond or glassy carbon) or ITO (as Anode or cathode) or less noble metals such as copper, stainless steel or nickel (as a cathode)
  • Fig. 1 shows various shapes of spirals.
  • A conical Archimedean spiral
  • B conical logarithmic spiral, view obliquely from the side.
  • C, D View of a working electrode (1) in the form of a conical Archimedean spiral from above.
  • the insulated conductors (3) are shown as thick dots.
  • C shows both insulated conductors (3) in the middle of the spiral
  • D shows the insulated conductor (3) connected to the outer side of the spiral outside the spiral.
  • FIG. 2 shows a preferred embodiment of a device according to the invention, by way of example with a working electrode (1) shaped as a conical Archimedean spiral.
  • the working electrode (1) is connected at a lower (5) and an upper (6) contact point with insulated conductors (3).
  • the working electrode (1) can be directly electrically heated via a symmetrical arrangement, alternating current (AC), preferably at least 50 kHz, being used as the heating current.
  • AC alternating current
  • the symmetrical contacting takes place by means of a bridge circuit (2). In the connection arms of the bridge circuit in each case a symmetrically designed inductance is provided (7).
  • This galvanostat or potentiostat can also be a simpler Stromversorguns réelle with two-pole output, on whose displays only the decomposition voltage between the working and counter electrode, and the electrolysis current are displayed.
  • a large area of the directly heatable working electrode (1) for electrochemical synthesis can be achieved by using a very long wire, for example of platinum or gold, or even parallel thin carbon pencils as working electrodes.
  • the working electrode is contacted as in the prior art at the ends, wherein a heating current of preferably at least 1000 Hz frequency, advantageously at least 20 kHz, better 50 kHz is used, so that a known bridge circuit or Throttling filter circuit can be used to separate the electrochemical from the heating circuit.
  • a Pt wire for example, 5 cm in length and 0, 1 mm diameter can be spirally wound on a cylindrical or preferably conical insulating cage made of glass, plastic or ceramic.
  • a working electrode may e.g. be used in a test tube as a cell for electrochemical synthesis.
  • a working electrode made of platinum has a resistance of 2 ohms and a length of 10 cm. Its diameter is 82.2 microns.
  • the electrode surface is as
  • the electrode length is 14.4 m, which is a
  • Electrode surface of 446 cm 2 result. This already allows syntheses, for example, in a 10 to 100 L reactor, ie on a pilot plant scale.
  • a wire for example made of platinum 1440 cm long and 1 mm in diameter has an advantageous heating resistance of 1 to 20, preferably 2 to 10 ohms and can be used in a larger cell, such as in Titanumsdorfstab.
  • the cage and the windings at the top are smaller in diameter (conical instead of cylindrical), so the working electrode has the shape of a conical spiral. This optimizes the thermal convection and achieves a uniform temperature control of the working electrode.
  • the electrochemical contact is in the middle as shown in FIG.
  • a device is used for a) selective oxidation of free amino groups to nitroso groups in proteins.
  • the entire electrolysis solution is heated for this purpose.
  • only the working electrode is heated from directly heated Glaskohlestiften, whereby the solution is simultaneously stirred thermoconvectively. External stirring and heating are not required. Yield and energy efficiency are improved.
  • the electrolysis cells can be structurally separated, or share a common cell space.
  • the latter allows the simultaneous study of immobilized enzymes in biocatalytic electrosynthesis at their own electrode temperature; the evaluation takes place via the measurement and evaluation of the electrolysis current.
  • external cooling is important to keep the electrolyte temperature constant at the desired value. Active cooling by Peltier elements can be helpful. Top-mounted coolers also support thermal convection.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)

Abstract

La présente invention concerne un procédé de préparation d'au moins un produit par synthèse électrochimique sur une électrode de travail (1) directement chauffée électriquement, procédé selon lequel au moins un produit de départ réagit sur l'électrode de travail (1) chauffée pour former ledit au moins un produit. L'invention concerne également l'utilisation d'une électrode de travail (1) directement chauffée électriquement pour la synthèse électrochimique d'au moins un produit. L'invention concerne par ailleurs une électrode de travail (1) conçue en particulier pour la synthèse électrochimique, notamment sous la forme d'une spirale tridimensionnelle, de préférence conique. L'invention a également pour objet la synthèse/régénération d'un cofacteur enzymatique sur une électrode de travail (1) selon l'invention.
PCT/DE2015/100403 2014-09-26 2015-09-25 Procédé et dispositif de synthèse électrochimique WO2016045665A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP15797246.4A EP3198060B1 (fr) 2014-09-26 2015-09-25 Procédé et dispositif de synthèse électrochimique
US15/514,233 US20170335474A1 (en) 2014-09-26 2015-09-25 Electrochemical synthesis method and device

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102014114047.8A DE102014114047A1 (de) 2014-09-26 2014-09-26 Verfahren und Vorrichtung zur elektrochemischen Synthese
DE102014114047.8 2014-09-26

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WO2016045665A3 WO2016045665A3 (fr) 2016-05-26

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EP3352371B1 (fr) 2017-01-19 2020-09-30 Methanology AG Système d'alimentation électrique pour un bâtiment autonome
DK3460101T3 (da) * 2017-09-21 2020-06-02 Hymeth Aps Elektrode til en elektrolyseproces

Citations (4)

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Publication number Priority date Publication date Assignee Title
US775123A (en) 1903-06-15 1904-11-15 Kristian Birkeland Apparatus for electrically treating gases.
DE102004017750A1 (de) 2004-04-06 2005-10-27 Flechsig, Gerd-Uwe, Dr. rer. nat. Analyse-Array mit heizbaren Elektroden und Verfahren für die chemische und biochemische Analytik
DE102006006347B3 (de) 2006-02-07 2007-08-23 Universität Rostock Sensorvorrichtung für ein elektrochemisches Messgerät und Verfahren zur Durchführung elektrochemischer Messungen
WO2013017635A1 (fr) 2011-08-04 2013-02-07 Universität Rostock Capteur électrochimique

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FR2765967B1 (fr) * 1997-07-11 1999-08-20 Commissariat Energie Atomique Dispositif d'analyse a puce comprenant des electrodes a chauffage localise
US7171111B2 (en) * 2002-07-03 2007-01-30 Sheldon Carlton W Method of heating water with rod shaped electrodes in a two-dimensional matrix

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Publication number Priority date Publication date Assignee Title
US775123A (en) 1903-06-15 1904-11-15 Kristian Birkeland Apparatus for electrically treating gases.
DE102004017750A1 (de) 2004-04-06 2005-10-27 Flechsig, Gerd-Uwe, Dr. rer. nat. Analyse-Array mit heizbaren Elektroden und Verfahren für die chemische und biochemische Analytik
DE102004017750B4 (de) 2004-04-06 2006-03-16 Flechsig, Gerd-Uwe, Dr. rer. nat. Analyse-Array mit heizbaren Elektroden
EP1743173A1 (fr) 2004-04-06 2007-01-17 Gerd-Uwe Flechsig Jeu ordonne d'echantillons pour analyse, muni d'electrodes chauffantes et procedes pour analyses chimiques et biochimiques
DE102006006347B3 (de) 2006-02-07 2007-08-23 Universität Rostock Sensorvorrichtung für ein elektrochemisches Messgerät und Verfahren zur Durchführung elektrochemischer Messungen
WO2013017635A1 (fr) 2011-08-04 2013-02-07 Universität Rostock Capteur électrochimique

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Title
FLECHSIG ET AL., LANGMUIR, vol. 21, 2005, pages 7848
P. GRÜNDLER ET AL., CHEM. PHYS. CHEM., vol. 10, 2009, pages 559
WACHHOLZ ET AL., ELECTROANALYSIS, vol. 19, 2007, pages 535 - 540
WACHHOLZ, DISSERTATION, 2009

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US20170335474A1 (en) 2017-11-23
DE102014114047A1 (de) 2016-03-31
EP3198060A2 (fr) 2017-08-02
EP3198060B1 (fr) 2020-12-02
WO2016045665A3 (fr) 2016-05-26

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