US20170335474A1 - Electrochemical synthesis method and device - Google Patents

Electrochemical synthesis method and device Download PDF

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US20170335474A1
US20170335474A1 US15/514,233 US201515514233A US2017335474A1 US 20170335474 A1 US20170335474 A1 US 20170335474A1 US 201515514233 A US201515514233 A US 201515514233A US 2017335474 A1 US2017335474 A1 US 2017335474A1
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working electrode
electrode
product
spiral
heated
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Gerd-Uwe Flechsig
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Universitaet Rostock
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Universitaet Rostock
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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 method for producing at least one product by electrochemical synthesis on a directly electrically-heated working electrode ( 1 ), in which at least one educt reacts on the heated working electrode ( 1 ) to the at least one product.
  • the invention also relates to the use of a directly electrically-heated working electrode ( 1 ) for the electrochemical synthesis of at least one product.
  • the invention relates in particular to a working electrode ( 1 ), particularly in the form of a three-dimensional, preferably conical spiral, designed for the electrochemical synthesis.
  • Another object of the invention is the synthesis/regeneration of an enzymatic cofactor on a working electrode ( 1 ) according to the invention.
  • heated working electrodes are used for trace analysis in voltammetry, amperometry/coulometry and potentiometry, and they can, for example, be directly heated by means of alternating current or indirectly by means of alternating current or direct current.
  • the working electrode can be constructed from several concentric or parallel layers, which are galvanically separated from one another, the outermost layer serving as an electrode and an inner layer serving as a heating element.
  • Indirect heating by means of heaters galvanically separated from the electrode is disadvantageous, because the construction of the sensors is more complicated, the temperature changes are generally slower because of the thermal inertia (due to the heat capacity) of the different layers, and the possibilities for miniaturization are limited.
  • Direct electrical heating of the working electrode and simultaneous interference-free electrochemical measurement can be performed according to the prior art by a so-called symmetrical arrangement or special filter circuits.
  • One variant of the directly-heated working electrode has a third contact for connection to the electrochemical measuring device, situated precisely in the middle between the two contacts which supply the heating current. This arrangement prevents interfering influences of the heating current on the measuring signals.
  • a disadvantage is the complex design with three contacts per working electrode, the thermal disturbance due to the heat-dissipating third contact and the complicated miniaturization.
  • a symmetrical contacting is effected by means of a bridge circuit, which allows direct heating (Wachholz et al., 2007, Electroanalysis 19, 535-540, in particular FIG.
  • the working electrode can be arranged so that the temperature distribution on the surface of the working electrode is uniform (DE 10 2004 017 750).
  • DE 10 2006 006 347 discloses advantageous directly electrically heatable electrodes.
  • the state of the art there are also array-like devices with a plurality of wire-shaped working electrodes which are to be independently heated, and which enable interference-free electrochemical measurement while simultaneously electrically-heating the electrodes, whereby the electrolyte solution can circulate freely around the electrodes.
  • the materials of the working electrodes can vary within an array. Similar to a conventional flat array, microliter drops can be deposited on the electrodes and surround them (WO 2013/017635).
  • microelectrodes heated as in the prior art can be used.
  • the working electrode must therefore be small in order to keep the mass conversion negligibly small, thus avoiding changes in the analytical solution, which is a prerequisite in analytical voltammetry and amperometry, and also in order to comply with the working range of the potentiostat-galvanostat.
  • electrochemical cells In order to be able to carry out electrochemical syntheses at elevated temperatures, electrochemical cells are generally used which are brought to the desired temperature by means of a thermostat with water as heat exchanger. The entire quantity of electrolyte is heated in the process.
  • a platinum electrode is generally used as the working electrode, as a cylinder of 3 cm in diameter and 5 cm in length.
  • the invention provides a process for producing at least one product by electrochemical synthesis on a directly electrically-heated working electrode ( 1 ), in which at least one educt reacts on the heated working electrode ( 1 ) to the at least one product.
  • the invention also provides the use of a directly electrically-heated working electrode ( 1 ) for the electrochemical synthesis of at least one product, in which at least one educt reacts on 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 with a heating current in the form of an alternating current, wherein the use of a bridge circuit, as described above, is particularly advantageous.
  • the symmetrical contacting and direct heating of the working electrode ( 1 ) can therefore be effected by means of, for example, the bridge circuit disclosed in Wachholz et al., 2007, Electroanalysis 19, 535-540, in particular FIG. 3 .
  • the working electrode ( 1 ) can have a first and a second contact for supplying the heating current, wherein the working electrode ( 1 ) is connected to a potentiostat via a third contact, wherein the connection of the third contact to the working electrode ( 1 ) is formed via a bridge circuit ( 2 ), which is connected to the first and second contact.
  • Suitable circuits are disclosed, for example, in DE 2006 006 347.
  • a heating current in the form of 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 instance for syntheses on a micro-scale, preferably 1 ⁇ 10 ⁇ 5 m 2 for instance on the half-micron scale or 1 ⁇ 10 ⁇ 4 m 2 for instance on the larger laboratory scale. Electrochemically-active surfaces up to an area of one or several square meters are also possible.
  • volume elements of the electrolyte solution are heated only very briefly when they come into contact with the working electrode ( 1 ) is particularly advantageous in the process according to the invention, the educts being converted electrochemically at the desired elevated temperature. Even undesired subsequent reactions at high temperature can be minimized by the rapid cooling of each volume element due to thermal convection. Thus, only the electrochemical reaction takes place at elevated temperature.
  • a process according to the invention can be used advantageously for various electrochemical syntheses, for example for oxidation, reduction, substitution, dehydrogenation, addition, cleavage, cyclization, dimerization, polymerisation, protonation, deprotonation or elimination.
  • the at least one product of the reaction may be, for example, a protein comprising a nitroso group, gluconic acid, sorbitol, D-arabinose, adipodinitrile, a regenerated cofactor such as NAD+ or NADP+. It is particularly advantageous 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. After synthesis on the heated working electrode, the product diffuses into the electrolyte, which itself is not heated to the reaction temperature.
  • Unstable in this context means that the stability at the reaction temperature is lower than the stability at a lower temperature (e.g., room temperature or 4° C.), especially for an, e.g. three- or ten-fold, lower stability relative to the difference in the reaction rate.
  • the stability may be analyzed by, e.g. half-life. It is possible to cool the electrolyte solution if this promotes the stability of the educt or product or the course of the reaction.
  • an electrochemical synthesis can for example proceed via a reaction of two educts to form one or two product(s) or via a reaction of one educt to form two products.
  • the reaction of the at least one educt to the at least one product can also be enzymatically catalyzed, wherein optionally the enzyme and/or a necessary cofactor is immobilized on the heated working electrode ( 1 ).
  • the educt(s), enzyme and/or cofactor can also be homogeneously distributed in the electrolyte solution.
  • a synthesis reaction takes place from at least one product catalyzed by an enzyme that requires a cofactor such as NAD+ or NADP+.
  • the regeneration of the cofactor which is necessary for a continuation of the reaction, takes place at the working electrode.
  • enzymatic catalysis it is, of course, also possible to synthesize a product which is unstable at the reaction temperature.
  • the temperature of the working electrode can be pulse-like for up to 300 ms, e.g. about 5-250 ms, 50-200 ms or 100-150 ms, but preferably less than 100 ms, above the boiling point of the electrolytes surrounding the electrode.
  • This has the advantage that only a small portion of the solution is heated for a short period of time. The thermal convection occurring briefly after the heating pulse makes stirring of the solution unnecessary.
  • the short period of heating is beneficial for the stability of educts and products and, if applicable, of enzymes which catalyze the reaction. In the case of unstable educts or products, this advantage plays an important role. Furthermore, any deposits on the working electrode are removed so that the latter cleans itself.
  • the process according to the invention makes it possible to monitor the material conversion of the reaction coulometrically.
  • coulometric tracking of the faraday mass conversion of a synthesis reaction is possible by measuring the electrolyte current strength and calculating the charge quantity/substance quantity as an integral of the current over time.
  • the invention also relates to a device which comprises two insulated conductors ( 3 ) which are connected to one another via a working electrode ( 1 ) which is thinner in relation to the conductors, the working electrode ( 1 ) being formed as an anode from an electrode material such as a wire of noble metal, in particular gold or platinum; or a rod of carbon, for example graphite, boron-doped diamond or glass-carbon; or 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, more preferably a three-dimensional spiral.
  • less noble metals such as copper, stainless steel or nickel can also be used as the cathode material.
  • the insulated conductors ( 3 ) can be, e.g. copper rods or other good electrical conductors, which are insulated, e.g. by a glass tube or by a plastic sheath, as is known in the art.
  • a flat Archimedian spiral can be placed on the ground and a screw (or helix) can be fitted into the shell as a curve.
  • the overlap curve of the spiral and screw is referred to as a conical spiral or cone-shaped space spiral.
  • an Archimedian spiral the distance to the center increases linearly to the increasing angle of its orbit. If this distance is projected as an angular distance to a pole on a spherical surface, an Archimedian spherical spiral is created. It is a line of finite length, and is not identical with the loxodrome, which by its construction method resembles the logarithmic spiral (Source: Wikipedia, see also FIG. 1 ). A central axis can be thought of through the center of the spiral.
  • the spiral is a conical spiral, in particular a conical Archimedeal spiral or an Archimedean spherical spiral or a loxodrome.
  • a section of such a spiral is sufficient, in particular in the case of spherical spirals, it is even preferred to use only a section which increases or decreases (i.e. not increases and then decreases) in diameter. Irregular spiral shapes are also possible. A particularly advantageous embodiment is shown in FIG. 2 .
  • a sufficient distance between sections of the working electrode ( 1 ) should be ensured in order to prevent short circuits.
  • the spacing is preferably uniform within the spiral.
  • the electrical contact points between the working electrode ( 1 ) and the insulated conductors ( 3 ) can be located approximately in the middle, i.e. on or near the central axis of the spiral.
  • the lower and upper contact points ( 5 , 6 ) are preferably slightly laterally offset from one another.
  • the contact point which is connected to the outermost side of the spiral most remote from the axis, can also be situated along the outer side of the spiral.
  • the three-dimensional spherical working electrode is oriented with respect to the insulated conductors and, as the case may be, the further structure of the device, such that the diameter of the spiral decreases from the bottom to the top.
  • the spiral working electrode When the spiral working electrode is vertically aligned along its central axis in the preferred three-dimensional spiral shape, and the device is used for electrochemical synthesis, the working electrode is hardly, or at best is not, vertically superimposed. Therefore, through heating of the working electrode the heated electrolyte solution does not meet overlying sections of the working electrode and additionally heat them. This ensures a uniform temperature of the working electrode, which is important for the course of the synthesis.
  • a further device which comprises two insulated conductors ( 3 ) which are connected to one another via a plurality of working electrodes ( 1 ) which are thinner in relation to the insulated conductors, wherein the working electrodes ( 1 ) are formed as an anode of a wire of noble metal, in particular gold or platinum; or a rod of carbon, for example graphite, boron-doped diamond or glass-carbon; or optically transparent conductive material such as ITO (indium-doped tin oxide) (an electrode material).
  • ITO indium-doped tin oxide
  • less noble metals such as copper, stainless steel or nickel can also be used as the cathode.
  • the working electrodes ( 1 ) are arranged so that no vertical superimposition of the working electrodes ( 1 ) takes place and that they
  • (b) preferably extend from a lower contact point ( 5 ) with one of the insulated conductors ( 3 ) to an upper contact point ( 6 ) offset vertically and optionally horizontally with the other insulated conductor ( 3 ), wherein the working electrodes ( 1 ) extend outwardly from the lower contact point ( 5 ), extend obliquely upwards in an intermediate section and extend inwards in an upper section towards the upper contact point ( 6 ), wherein the inclination in the middle section is arranged so that no vertical superimposition of the working electrode sections ( 1 ) or the working electrodes ( 1 ) occurs.
  • the working electrode essentially has a stepladder-like shape, as in the case of a rung wall, the struts of which form the insulated conductors ( 3 ) and which are set obliquely in order to prevent a vertical superposition of the working electrodes (rungs).
  • the struts which form the insulated conductors ( 3 ) and which are set obliquely in order to prevent a vertical superposition of the working electrodes (rungs).
  • parallel glass charcoal or graphite rods which are arranged ladder-like, but obliquely. These parallel rods are connected by insulated conductors, resulting in a grid-shaped working electrode.
  • the rods can be fixed, e.g. by attachment to an insulating grid or cage.
  • the grid or cage can be a stretched, e.g. a flat or e.g. cylindrical, shape.
  • screen printing electrodes e.g. of carbon in parallel form, is possible.
  • the insulating carrier ( 7 ) can, for example, be a cage or a grid. Preferably, free circulation of the electrolyte by the support ( 7 ) is not severely restricted.
  • the insulating support preferably consists of or comprises an insulating material, the material being glass, ceramic or plastic, e.g. Polytetrafluoroethylene (PTFE, Teflon®). 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 ) has a surface area of at least 1 ⁇ 10 ⁇ 6 m 2 , preferably 1 ⁇ 10 ⁇ 5 m 2 or 1 ⁇ 10 ⁇ 4 m 2 .
  • the diameter may be e.g. about 0.05-5 mm, preferably 0.1-1 mm.
  • the length may be about 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 specific resistance of the electrode material, so that a reasonable resistance range is maintained: the resistance between the two heating current contacts ( 5 ) and ( 6 ) should be determined, e.g. approximately 0.5 to 20 Ohm, preferably 1 to 10 Ohm.
  • the voltage drop between the contacts is on the one hand not too great, on the other hand, the resistance can still be easily measured by means of electronics, and thus the heating power can be automatically regulated (Flechsig, Gründner, Wang, 2004, EP 1743173, DE 10 2004 017 750 B4).
  • Example: the platinum working electrode has a resistance of 2 Ohm and a length of 10 cm. Then the diameter must be 82.2 microns. The electrode surface is then 25.8 mm 2 as a cylinder jacket surface.
  • the electrode length would have to be 14.4 m, resulting in an electrode surface of 446 cm 2 . That would be pilot plant scale.
  • the working electrode ( 1 ) in the device according to the invention is directly heated by means of a symmetrical arrangement with a heating current in the form of an alternating current.
  • the symmetrical contacting preferably occurs via a bridge circuit ( 2 ), as explained above.
  • a symmetrically arranged inductance is provided in the connecting arms of the bridge circuit ( 7 ).
  • the working electrode ( 1 ) can be connected with a galvanostat or a potentiostat, a reference electrode (REF) and a counterelectrode (AUX) which either functions as an anode or a cathode, depending on whether a reduction or an oxidation is running on the working electrode.
  • This galvanostat or potentiostat can also be a simpler power supply device with a two-pole output, on the displays of which only the decomposition voltage between the working electrode and the counterelectrode, as well as the electrolysis current, are indicated.
  • the counterelectrode (AUX) in the device according to the invention is arranged with a distance to the working electrode of at least 1 mm, preferably at least 5 mm, so that the thermal convection around and above the working electrode does not lead to a mixing of the space around the counterelectrode, preferably it is beneath the working electrode.
  • This avoids the reverse reaction of the product to the educt at the counterelectrode.
  • unwanted products are prevented from coming from the counterelectrode 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 carry out a cathodic reduction in a chloride-containing solution at a strongly negative potential.
  • a cooler at the bottom of the cell, e.g. a cooling Peltier element.
  • the device can 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 proceeds on the directly heated working electrode of a device according to the invention, in particular a device comprising two insulated conductors ( 3 ) which are connected to one another via a working electrode ( 1 ) which is thinner in relation to the conductors, wherein the working electrode ( 1 ) is a wire of an electrode material such as gold, platinum and carbon (e.g. graphite, boron doped diamond or glass carbon) or ITO (as anode or cathode) or even less noble metals such as copper, stainless steel or nickel (as cathode), the working electrode ( 1 ) having the form of a spiral, preferably a three-dimensional spiral.
  • an electrode material such as gold, platinum and carbon (e.g. graphite, boron doped diamond or glass carbon) or ITO (as anode or cathode) or even less noble metals such as copper, stainless steel or nickel (as cathode)
  • the working electrode ( 1 ) having the form of a spiral, preferably a
  • 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 on a directly electrically heatable working electrode, preferably on the directly heated working electrode of a device according to the invention. It is also preferable to use a device which comprises two insulated conductors ( 3 ) which are connected to one another by means of a thinner working electrode ( 1 ) in relation to the conductors, the working electrode ( 1 ) being a wire of an electrode material such as gold, platinum and carbon (e.g.
  • the working electrode ( 1 ) is in the form of a spiral, preferably a three-dimensional spiral.
  • FIG. 1 shows various forms of spirals.
  • A conical Archimedean spiral
  • B conical logarithmic spiral; in each case viewed 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 center of the spiral
  • D) shows the insulated conductors ( 3 ) with one connected to the outer side of the spiral.
  • FIG. 2 shows a preferred embodiment of a device according to the invention, with a working electrode ( 1 ) shaped as a conical Achimedean spiral.
  • the working electrode ( 1 ) is connected to insulated conductors ( 3 ) at a lower ( 5 ) and an upper ( 6 ) contact point.
  • the working electrode ( 1 ) is directly electrically heatable via a symmetrical arrangement, with alternating current (AC), preferably at least 50 kHz, being used as the heating current.
  • AC alternating current
  • the symmetrical contacting is effected by means of a bridge circuit ( 2 ).
  • a symmetrically arranged inductance is provided in the connection arms of the bridge circuit ( 7 ).
  • the working electrode ( 1 ) is or can be connected with a galvanostat or a potentiostat, a reference electrode (REF) and a counterelectrode (AU/AUX), which functions either as an anode or a cathode, depending on whether a reduction or an oxidation takes place at the working electrode.
  • This galvanostat or potentiostat can also be a simple power supply device with a two-pole output, on whose displays merely the decomposition voltage between the working electrode and the counterelectrode, as well as the electrolytic current, are indicated.
  • a large area of the directly heatable working electrode ( 1 ) for electrochemical synthesis can be achieved in that a very long wire e.g. out of platinum or gold, or else parallel thin carbon rods, can be used as working electrodes.
  • the working electrode is contacted at the ends as in the prior art, whereby a heating current of preferably at least 1000 Hz frequency, advantageously at least 20 kHz, more preferably 50 kHz, is used so that a bridge circuit or a choke filter circuit known per se for separating the electrochemical circuit from the heating circuit can be used.
  • a Pt wire of, for example, 5 cm in length and 0.1 mm in diameter can be spirally wound onto a cylindrical or preferably conical insulating cage made of glass, plastic or ceramic.
  • a working electrode can be used, e.g. in a reagent glass, as a cell for electrochemical synthesis.
  • a working electrode of platinum has a resistance of 2 ohm and a length of 10 cm. Its diameter is 82.2 microns.
  • the electrode surface area is 25.8 mm 2 as the cylinder surface area.
  • the electrode length is 14.4 m, resulting in an electrode surface area of 446 cm 2 .
  • a wire e.g. of platinum of 1440 cm in length 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, e.g. in the pilot-plant scale.
  • the working electrode thus has the shape of a conical spiral. This optimizes thermal convection and achieves a uniform temperature control of the working electrode.
  • the electrochemical contact is located in the center, as shown in FIG. 2 .
  • a device according to the invention is used for
  • Oxidation of aldehyde groups in sugars to gluconic acid by an electrochemically prepared oxidizing agent e.g., hypobromide of bromide
  • an electrochemically prepared oxidizing agent e.g., hypobromide of bromide
  • heated carbon rod electrodes of graphite or glass-carbon can be used.
  • the electrolysis cells can be structurally separated from one another or can share a common cell space.
  • the latter permits the simultaneous study of immobilized enzymes in biocatalytic electrosynthesis at the respective electrode temperature; the evaluation being carried out by means of the measurement and evaluation of the electrolysis current. Cooling from the outside is particularly important for small cell volumes, in order to keep the electrolyte temperature constant at the desired value. Active cooling by Peltier elements can be helpful. Coolers from above 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)
US15/514,233 2014-09-26 2015-09-25 Electrochemical synthesis method and device Abandoned US20170335474A1 (en)

Applications Claiming Priority (3)

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
PCT/DE2015/100403 WO2016045665A2 (de) 2014-09-26 2015-09-25 Verfahren und vorrichtung zur elektrochemischen synthese

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EP (1) EP3198060B1 (de)
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Cited By (1)

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Publication number Priority date Publication date Assignee Title
US20200216969A1 (en) * 2017-09-21 2020-07-09 Hymeth Aps Electrode for an electrolysis process

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EP3352371B1 (de) 2017-01-19 2020-09-30 Methanology AG Energieversorgungssystem für ein autarkes gebäude

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US775123A (en) 1903-06-15 1904-11-15 Kristian Birkeland Apparatus for electrically treating gases.
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
DE102004017750B4 (de) 2004-04-06 2006-03-16 Flechsig, Gerd-Uwe, Dr. rer. nat. Analyse-Array mit heizbaren Elektroden
DE102006006347B3 (de) 2006-02-07 2007-08-23 Universität Rostock Sensorvorrichtung für ein elektrochemisches Messgerät und Verfahren zur Durchführung elektrochemischer Messungen
DE102011109402A1 (de) 2011-08-04 2013-02-07 Universität Rostock Elektrochemischer Sensor

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200216969A1 (en) * 2017-09-21 2020-07-09 Hymeth Aps Electrode for an electrolysis process
US11732369B2 (en) * 2017-09-21 2023-08-22 Hymeth Aps Electrode for an electrolysis process

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EP3198060B1 (de) 2020-12-02

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