KR20180020763A - Electrochemical reduction apparatus of carbon dioxide and/or carbon monoxide and electrochemical reduction method of carbon dioxide and/or carbon monoxide using the apparatus - Google Patents

Abstract

The present invention relates to an electrochemical reduction device for carbon dioxide and/or carbon monoxide, which operates by periodically switching a direction of current and/or polarity of voltage applied to a working electrode and a counter electrode, respectively. The present invention further relates to an electrochemical reduction method for carbon dioxide and/or carbon monoxide using the electrochemical reduction device.

Description

FIELD OF THE INVENTION [0001] The present invention relates to an electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide, and an electrochemical reduction method for carbon dioxide and / or carbon monoxide using the apparatus. USING THE APPARATUS}

The present invention relates to an electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide, which is operated by periodically switching the polarity of a voltage applied to each of a working electrode and a counter electrode and / or a direction of a current, and an apparatus for reducing carbon dioxide and / To a method for electrochemical reduction of carbon monoxide.

Carbon-based materials on the Earth form carbon cycles in many forms and maintain a certain amount and balance. However, this balance is breaking due to the increase in atmospheric carbon dioxide (CO ₂ ), one of the carbon-forming substances.

The increase in atmospheric carbon dioxide concentration is caused by the increased carbon dioxide emissions since industrialization. Since the first observation of carbon dioxide emissions in 1965 (about 12 billion tons), the carbon dioxide emissions continue to increase, reaching around 34 billion tons of carbon dioxide And the increase in CO2 emissions is expected to continue in a structure that depends on most energy for fossil fuels as it is now.

Research on the removal of atmospheric carbon dioxide is being actively carried out around the world, recognizing the danger of the rapid increase of carbon dioxide in the atmosphere. As a method for removing the carbon dioxide, research has been conducted to produce hydrogen or the like by catalytic reduction of carbon dioxide, electrochemical reduction or the like.

In this regard, Korean Patent No. 10-0856569 discloses the conversion of carbon dioxide into acetic acid, polycarbonate, etc. through a catalytic chemical method.

However, there is still a need to develop a technique for producing hydrogen and other useful compounds at a relatively high selectivity and yield by electrochemical reduction of carbon dioxide.

The present invention relates to an electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide, which is operated by periodically switching the polarity of a voltage applied to each of a working electrode and a counter electrode and / or a direction of a current, and an apparatus for reducing carbon dioxide and / Thereby providing an electrochemical reduction method of carbon monoxide.

However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.

According to a first aspect of the present invention, there is provided a plasma processing apparatus including: an oxidation electrode unit including a reduction electrode unit including a working electrode and a counter electrode; A first chamber for supplying carbon dioxide and / or a reactant to the reduction electrode unit; An optional second chamber for supplying carrier gas to the oxidation electrode portion if necessary; And a power supply for applying a voltage and a current to the working electrode and the counter electrode, respectively, wherein a polarity of a voltage applied to the working electrode and the counter electrode, and / or a direction of the current are periodically switched Carbon monoxide and / or carbon monoxide.

According to a second aspect of the present invention, there is provided an electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide comprising a reducing electrode portion including a working electrode and an oxidizing electrode portion including a counter electrode, and supplies carbon dioxide and / or a reactant to the reducing electrode portion And selectively supplying a carrier gas to the oxidation electrode unit and switching the polarity of the voltage applied to the working electrode and the counter electrode and / or the direction of the current to the reduction electrode unit Carbon monoxide and / or carbon monoxide, comprising reducing carbon dioxide and / or carbon monoxide.

According to one embodiment of the present invention, in the electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide, the polarity of the voltage applied to the working electrode and the counter electrode and / or the direction of the current are periodically switched, The proportion of low value added hydrogen can be reduced, and the proportion of materials containing relatively high value-added carbon can be increased. In particular, alcohols present as liquids at room temperature can be obtained as the product of the electrochemical reduction of carbon dioxide and / or carbon monoxide.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic diagram showing a batch electrochemical reduction apparatus of carbon dioxide and / or carbon monoxide, using an applied voltage and / or current switching, in one embodiment of the invention.
2 is a schematic diagram showing a batch type electrochemical reduction apparatus of carbon dioxide and / or carbon monoxide as a comparative example without switching of applied voltage and / or current.
FIG. 3 is a schematic diagram illustrating a circulating electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide using switching of an applied voltage and / or current, in one embodiment of the present invention. FIG.
Fig. 4 is a schematic diagram showing a circulating electrochemical reduction apparatus of carbon dioxide and / or carbon monoxide as a comparative example without switching of applied voltage and / or current.
FIG. 5 is a schematic diagram illustrating a PEM type system electrochemical reduction apparatus of carbon dioxide and / or carbon monoxide utilizing switching of applied voltage and / or current, in one embodiment of the present invention.
Fig. 6 is a schematic view showing, as a comparative example, a PEM type system electrochemical reduction apparatus of carbon dioxide and / or carbon monoxide without switching of applied voltage and / or current.
Fig. 7 is a schematic view showing main products and by-products when the electrochemical reduction apparatus of each carbon dioxide and / or carbon monoxide is used in the examples and the comparative examples of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is " on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise. The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term " combination thereof " included in the expression of the machine form means one or more combinations or combinations selected from the group consisting of the constituents described in the expression of the machine form, And the like.

According to a first aspect of the present invention, there is provided a plasma processing apparatus including: an oxidation electrode unit including a reduction electrode unit including a working electrode and a counter electrode; A first chamber for supplying carbon dioxide and / or a reactant to the reduction electrode unit; An optional second chamber for supplying carrier gas to the oxidation electrode portion if necessary; And a power supply for applying a voltage and a current to the working electrode and the counter electrode, respectively, wherein a polarity of a voltage applied to the working electrode and the counter electrode, and / or a direction of the current are periodically switched Carbon monoxide and / or carbon monoxide.

In one embodiment of the present invention, the polarity and magnitude of the voltage applied to the working electrode and the counter electrode, respectively, and / or the direction and intensity of the current may be periodically switched.

In one embodiment of the present invention, the carbon monoxide generated during the reduction reaction of carbon dioxide using the electrochemical reduction apparatus may be reduced in the electrochemical reduction apparatus.

In one embodiment of the present application, the working electrode and the counter electrode each independently comprise a material selected from the group consisting of a metal, an alloy, a non-metal, an oxide of the metal or alloy, a sulfide, a phosphide, a nitride, .

In one embodiment of the present invention, when the material of the working electrode and the counter electrode is a metal, the metal may be selected from the group consisting of copper (Cu), silver (Ag), gold (Au), platinum (Pt), palladium (Pb), Fe (Fe), Co, Ir, Rh, Ni, Sn, and combinations thereof. But is not limited thereto.

In one embodiment of the present invention, when the material of the working electrode and the counter electrode is a non-metal, the non-metal may include graphite, graphitic carbon, graphene, Fe-doped carbon, N- But may include materials selected from the group consisting of N-doped carbon, carbon modified by functional molecules, carbon nanotubes, mesoporous carbon, boron-nitrogen compounds, and combinations thereof. But is not limited to.

In one embodiment of the present invention, the materials of the working electrode and the counter electrode may be uniformly or non-uniformly blended with each other, and may be a laminated structure. In addition, the materials may be in the form of particles and may have various sizes and may be mixed as various structures.

In one embodiment of the present invention, the electrochemical reduction apparatus for carbon dioxide may further include a reference electrode positioned at the reduction electrode unit.

In one embodiment of the present invention, the electrolyte solution injected into the reducing electrode portion and the oxidizing electrode portion is independently a bicarbonate solution, a carbonate solution, a phosphate solution, a biphosphate solution A borate solution, an ionic liquid, a sulfuric acid solution, a phosphoric acid solution, an alkali solution, a buffer solution, a molten salt, and combinations thereof. But is not limited to.

In one embodiment of the present invention, the reducing electrode portion and the oxidizing electrode portion may be separated from each other by a membrane, and the membrane may be a cation exchange membrane, anion exchange membrane, brassiere, porous glass, ceramic, metal, metal oxide, But are not limited to, membranes selected from the group consisting of membranes, membranes, and combinations thereof. For example, the polymer-nanoparticle mixed membrane may be a nanoparticle-reinforced membrane such that the organic matter generated at one electrode portion can not penetrate into the other electrode portion.

In an embodiment of the present invention, when the working electrode and the counter electrode are both made of copper, the electrochemical reduction apparatus for the carbon dioxide and / or carbon monoxide may not include the membrane, but is not limited thereto.

In an embodiment of the present invention, the reactant injected together with the carbon dioxide is not particularly limited as long as it is an electrochemically reactive compound, for example, water, carbon monoxide, chemical additives, and combinations thereof And the like.

In one embodiment of the invention, the carrier gas selectively supplied to the oxidation electrode portion includes a gas selected from the group consisting of, for example, carbon dioxide, air, hydrogen, helium, nitrogen, and combinations thereof , But is not limited thereto.

In one embodiment of the present invention, the product produced by the reduction reaction in the carbon dioxide electrochemical reduction apparatus may be different depending on the reactants, for example, hydrogen, carbon monoxide, hydrocarbons, alcohols, aldehydes, And combinations thereof. ≪ RTI ID = 0.0 > [0040] < / RTI >

In one embodiment of the invention, the hydrocarbons may be, for example, hydrocarbons having 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms, For example, the aldehydes may be, for example, R ', wherein R' is an alcohol represented by ROH, wherein R is an alkyl group having 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms, CHO (R 'is an alkyl group having 1 to 10 carbon atoms, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms). The organic acids may be, for example, organic acids represented by R " COOH (R " is an alkyl group having 1 to 10 carbon atoms, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms) .

In one embodiment of the invention, the voltages applied to the working electrode and the counter electrode, respectively, may be about -10 V to about -1 V, and about 0.5 V to about 10 V, but are not limited thereto. For example, the voltage applied to the working electrode may range from about -10 V to about -1 V, from about -8 V to about -1 V, from about -6 V to about -1 V, from about -4 V to about -1 V, about -2 V to about -1 V, about -10 V to about -2 V, about -10 V to about -4 V, about -10 V to about -6 V, or about -10 V to about- 8 V; The voltage applied to the counter electrode may range from about 0.5 V to about 10 V, from about 1 V to about 10 V, from about 3 V to about 10 V, from about 5 V to about 10 V, from about 7 V to about 10 V, from about 9 From about 0.5 V to about 7 V, from about 0.5 V to about 5 V, from about 0.5 V to about 3 V, or from about 0.5 V to about 1 V, But is not limited thereto.

In one embodiment of the present invention, the voltages applied to the working electrode and the counter electrode may be different from each other. In addition, when the electrochemical reduction apparatus does not include a reference electrode, the reference potential of the voltage applied to the working electrode and the counter electrode may be 0 V. When the reference electrode is included, Lt; / RTI >

In one embodiment of the present invention, the voltage may alternately be applied to the working electrode and the counter electrode, respectively, and may be applied to the working electrode and the counter electrode for about 1 second to about 50 seconds, respectively, It is not. For example, the time for which a voltage can be applied to each of the working electrode and the counter electrode is about 1 second to about 50 seconds, about 5 seconds to about 50 seconds, about 10 seconds to about 50 seconds, about 15 seconds to about From about 30 seconds to about 50 seconds, from about 20 seconds to about 50 seconds, from about 25 seconds to about 50 seconds, from about 30 seconds to about 50 seconds, from about 35 seconds to about 50 seconds, from about 40 seconds to about 50 seconds, From about 1 second to about 45 seconds, from about 1 second to about 40 seconds, from about 1 second to about 35 seconds, from about 1 second to about 30 seconds, from about 1 second to about 25 seconds, from about 1 second to about 20 seconds, From about 1 second to about 15 seconds, from about 1 second to about 10 seconds, or from about 1 second to about 5 seconds.

In one embodiment, the currents applied to the working electrode and the counter electrode, respectively, are in the range of about -2,000 mA / cm ² to about -1 mA / cm ² , and about 1 mA / cm ² to about 2,000 mA / ² , but is not limited thereto. For example, the current that can be applied to the working electrode is about -2,000 mA / cm ² to about -1 mA / cm ² , about -1,500 mA / cm ² to about -1 mA / cm ² , about -1,000 mA / cm ² and about -1 mA / cm ^2, from about -500 mA / cm ² and about -1 mA / cm ^2, from about -400 mA / cm ² and about -1 mA / cm ^2, from about -300 mA / cm ² and about -1 mA / cm ^2, from about -200 mA / cm ² and about -1 mA / cm ^2, from about -100 mA / cm ² and about -1 mA / cm ^2, from about -50 mA / cm ² to about -1 mA / cm ^2, from about -2,000 mA / cm ² to about -50 mA / cm ^2, from about -2,000 mA / cm ² to about -100 mA / cm ^2, from about -2,000 mA / cm ² to about - 200 mA / cm ^2, from about -2,000 mA / cm ² to about -300 mA / cm ^2, from about -2,000 mA / cm ² to about -400 mA / cm ^2, from about -2,000 mA / cm ² to about -500 mA / cm ² , about -2,000 mA / cm ² to about -1,000 mA / cm ² , or about -2,000 mA / cm ² to about -1,500 mA / cm ² . Also, the current that can be applied to the counter electrode is about 1 mA / cm ² to about 2,000 mA / cm ² , about 50 mA / cm ² to about 2,000 mA / cm ² , about 100 mA / cm ² to about 2,000 mA / cm ^2, about 200 mA / cm ² to about 2,000 mA / cm ^2, about 300 mA / cm ² to about 2,000 mA / cm ^2, about 400 mA / cm ² to about 2,000 mA / cm ^2, about 500 mA / cm ² to about 2,000 mA / cm ^2, from about 1,000 mA / cm ² to about 2,000 mA / cm ^2, from about 1,500 mA / cm ² to about 2,000 mA / cm ^2, about 1 mA / cm ² to about 1,500 mA / cm ^2, about 1 mA / cm ² to about 1,000 mA / cm ^2, about 1 mA / cm ² to about 500 mA / cm ^2, about 1 mA / cm ² to about 400 mA / cm ^2, about 1 mA / cm ² to about 300 mA / cm ^2, about 1 mA / cm ² to about 200 mA / cm ^2, about 1 mA / cm ² to about 100 mA / cm ^2, or about 1 mA / cm ² to about 50 mA / cm ² But is not limited thereto.

In one embodiment of the present invention, the magnitudes of the currents applied to the working electrode and the counter electrode may be different from each other. If the electrochemical reduction apparatus does not include the reference electrode, the reference current of the current applied to the working electrode and the counter electrode may be 0 mA / cm ^2. If the reference electrode is included, May be the current of the reference electrode.

In one embodiment of the present invention, the current may alternately be applied to the working electrode and the counter electrode, respectively, and may be applied to the working electrode and the counter electrode for about 1 second to about 50 seconds, respectively, It is not. For example, the time during which the current can be applied to each of the working electrode and the counter electrode is about 1 second to about 50 seconds, about 5 seconds to about 50 seconds, about 10 seconds to about 50 seconds, about 15 seconds to about From about 30 seconds to about 50 seconds, from about 20 seconds to about 50 seconds, from about 25 seconds to about 50 seconds, from about 30 seconds to about 50 seconds, from about 35 seconds to about 50 seconds, from about 40 seconds to about 50 seconds, From about 1 second to about 45 seconds, from about 1 second to about 40 seconds, from about 1 second to about 35 seconds, from about 1 second to about 30 seconds, from about 1 second to about 25 seconds, from about 1 second to about 20 seconds, From about 1 second to about 15 seconds, from about 1 second to about 10 seconds, or from about 1 second to about 5 seconds.

In one embodiment, the electrochemical reduction device for carbon dioxide and / or carbon monoxide may be a batch, circulation, continuous, polymer electrolyte membrane (PEM) type system, or combinations thereof And the like.

1, when the electrochemical reduction apparatus 101 for the carbon dioxide and / or carbon monoxide is a batch type, the reduction electrode unit 110 and / The oxidation electrode unit 120 may be separated. Each of the reducing electrode unit 110 and the oxidizing electrode unit 120 includes an electrolyte solution 190. The working electrode 140 and the oxidizing electrode unit 120 include the working electrode 140 and the counter electrode 150, Respectively. Carbon dioxide and / or reactant supplied from the first chamber 170 is supplied to the reduction electrode unit 110 and a carrier gas is selectively supplied to the oxidation electrode unit 120 from the second chamber 180, if necessary. Unlike the comparative device of FIG. 2, the two electrode units are connected to each other by a power supply unit 160, and the working electrode 140 (not shown) connected by the power supply unit 160, And the counter electrode 150, and / or the direction of the current are periodically switched with time. The unnecessary gas generated during the reaction is discharged through the gas outlet 200. The product produced by applying the voltage and current and the electrolyte solution containing the product and the electrolyte solution are collected after the reaction is continued for a predetermined time, and a new reaction can be performed by replacing with a new electrolyte solution.

3, when the electrochemical reduction apparatus 101 for the carbon dioxide and / or carbon monoxide is a circulating type, the carbon dioxide and / or the reactant and the electrolyte are continuously supplied from the first chamber 170 And the product produced by the electrolyte and the reduction reaction is supplied to the first product collecting chamber 210 through the discharge pipe located in the upper portion of the apparatus, . ≪ / RTI > At the same time or at a different point in time, the carrier gas and / or electrolyte is continuously supplied from the second chamber 180 to the oxidizing electrode portion 120 through the inlet pipe located at the lower portion of the apparatus, and the carrier gas and / The electrolyte may be continuously collected into the second product collection chamber 220 through a discharge line located at the top of the apparatus. The reduction electrode unit 110 includes a working electrode 140 and the oxidation electrode unit 120 includes a counter electrode 150. The two electrode units may be separated from each other by a membrane 130 . A plate 230 is positioned on the outer side of the two electrode units, and spacers 240 are disposed on the upper and lower sides of the plate 230, respectively. The working electrode 140 and the counter electrode 150 are connected to each other by a power supply unit 160. Unlike the comparative example apparatus of FIG. 4, the voltage and current are not constant, And / or the direction of the current applied to each of the working electrode and the counter electrode connected to each other by the switching unit (not shown) is periodically switched with time.

5, when the electrochemical reduction apparatus for carbon dioxide is a polymer electrolyte membrane (PEM) type system, carbon dioxide and / or reactant and electrolyte are continuously supplied from the first chamber And the product produced by the electrolyte and the reduction reaction is continuously collected into the first product collection chamber through the discharge pipe located at the top of the device have. At the same time or at a different point in time, the carrier gas and / or the electrolyte are continuously supplied from the second chamber to the oxidizing electrode portion through the inlet pipe located at the lower portion of the apparatus, and the carrier gas and / To the second product collection chamber through a discharge line located in the second product collection chamber. The reduction electrode unit may include a working electrode and the oxidation electrode unit may include a counter electrode. The mesh electrode may be attached to the working electrode and the counter electrode. The two electrode portions may be separated from each other by a membrane. A plate is positioned on the outer side of the two electrode portions, and a gasket spacer is disposed on the upper and lower portions, respectively. The mesh electrodes attached to the working electrode and the counter electrode are connected to each other by a power supply unit. Unlike the comparative example apparatus of FIG. 6, the voltage and current are not constant, The polarity of the voltage applied to each of the mesh electrode to which the electrode is attached and the mesh electrode to which the counter electrode is attached, and / or the direction of the current are periodically switched with time.

In one embodiment of the present invention, the electrochemical reduction apparatus for the carbon dioxide may be plural, and may be connected in series, parallel, or stacking structure, but is not limited thereto.

According to a second aspect of the present invention, there is provided an electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide comprising a reducing electrode portion including a working electrode and an oxidizing electrode portion including a counter electrode, and supplies carbon dioxide and / or a reactant to the reducing electrode portion And selectively supplying a carrier gas to the oxidation electrode unit and switching the polarity of the voltage applied to the working electrode and the counter electrode and / or the direction of the current to the reduction electrode unit Carbon monoxide and / or carbon monoxide, comprising reducing carbon dioxide and / or carbon monoxide. Although the detailed description of the parts overlapping with the first aspect of the present application is omitted, the description of the first aspect of the present invention can be applied equally to the second aspect.

In one embodiment of the present invention, the polarity and magnitude of the voltage applied to the working electrode and the counter electrode, respectively, and / or the direction and intensity of the current may be periodically switched.

In one embodiment of the present invention, the carbon monoxide generated during the reduction reaction of carbon dioxide using the electrochemical reduction apparatus may be reduced in the electrochemical reduction apparatus.

In one embodiment of the present application, the working electrode and the counter electrode each independently comprise a material selected from the group consisting of a metal, an alloy, a non-metal, an oxide of the metal or alloy, a sulfide, a phosphide, a nitride, .

In one embodiment of the present invention, when the material of the working electrode and the counter electrode is a metal, the metal may be selected from the group consisting of copper (Cu), silver (Ag), gold (Au), platinum (Pt), palladium (Pb), Fe (Fe), Co, Ir, Rh, Ni, Sn, and combinations thereof. But is not limited thereto.

In one embodiment of the present invention, when the material of the working electrode and the counter electrode is a non-metal, the non-metal may include graphite, graphitic carbon, graphene, Fe-doped carbon, N- But may include materials selected from the group consisting of N-doped carbon, carbon modified by functional molecules, carbon nanotubes, mesoporous carbon, boron-nitrogen compounds, and combinations thereof. But is not limited to.

In one embodiment of the present invention, the materials of the working electrode and the counter electrode may be uniformly or non-uniformly blended with each other, and may be a laminated structure. In addition, the materials may be in the form of particles and may have various sizes and may be mixed as various structures.

In one embodiment of the present invention, the electrochemical reduction apparatus for carbon dioxide may further include a reference electrode positioned at the reduction electrode unit.

In one embodiment of the present invention, the electrolyte solution injected into the reducing electrode portion and the oxidizing electrode portion is independently a bicarbonate solution, a carbonate solution, a phosphate solution, a biphosphate solution A borate solution, an ionic liquid, a sulfuric acid solution, a phosphoric acid solution, an alkali solution, a buffer solution, a molten salt, and combinations thereof. But is not limited to.

In one embodiment of the present invention, the reducing electrode portion and the oxidizing electrode portion may be separated from each other by a membrane, and the membrane may be a cation exchange membrane, anion exchange membrane, brassiere, porous glass, ceramic, metal, metal oxide, But are not limited to, membranes selected from the group consisting of membranes, membranes, and combinations thereof. For example, the polymer-nanoparticle mixed membrane may be a nanoparticle-reinforced membrane such that the organic matter generated at one electrode portion can not penetrate into the other electrode portion.

In an embodiment of the present invention, when the working electrode and the counter electrode are both made of copper, the electrochemical reduction apparatus for the carbon dioxide and / or carbon monoxide may not include the membrane, but is not limited thereto.

In an embodiment of the present invention, the reactant injected together with the carbon dioxide is not particularly limited as long as it is an electrochemically reactive compound, for example, water, carbon monoxide, chemical additives, and combinations thereof And the like.

In one embodiment of the invention, the carrier gas selectively supplied to the oxidation electrode portion includes a gas selected from the group consisting of, for example, carbon dioxide, air, hydrogen, helium, nitrogen, and combinations thereof , But is not limited thereto.

In one embodiment of the present invention, the product produced by the reduction reaction in the carbon dioxide electrochemical reduction apparatus may be different depending on the reactants, for example, hydrogen, carbon monoxide, hydrocarbons, alcohols, aldehydes, And combinations thereof. ≪ RTI ID = 0.0 > [0040] < / RTI >

In one embodiment of the invention, the hydrocarbons may be, for example, hydrocarbons having 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms, For example, the aldehyde may be, for example, an alcohol represented by ROH (wherein R is an alkyl group having 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms) 'CHO (R' is an alkyl group having 1 to 10 carbon atoms, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms). The organic acids may be, for example, an organic acid group represented by R " COOH (wherein R " is an alkyl group having 1 to 10, 1 to 8, 1 to 6, 1 to 4, or 1 to 2 carbon atoms) have.

In one embodiment of the invention, the voltages applied to the working electrode and the counter electrode, respectively, may be about -10 V to about -1 V, and about 0.5 V to about 10 V, but are not limited thereto. For example, the voltage applied to the working electrode may range from about -10 V to about -1 V, from about -8 V to about -1 V, from about -6 V to about -1 V, from about -4 V to about -1 V, about -2 V to about -1 V, about -10 V to about -2 V, about -10 V to about -4 V, about -10 V to about -6 V, or about -10 V to about- 8 V; The voltage applied to the counter electrode may range from about 0.5 V to about 10 V, from about 1 V to about 10 V, from about 3 V to about 10 V, from about 5 V to about 10 V, from about 7 V to about 10 V, from about 9 From about 0.5 V to about 7 V, from about 0.5 V to about 5 V, from about 0.5 V to about 3 V, or from about 0.5 V to about 1 V, But is not limited thereto.

In one embodiment of the present invention, the voltages applied to the working electrode and the counter electrode may be different from each other. In addition, when the electrochemical reduction apparatus does not include a reference electrode, the reference potential of the voltage applied to the working electrode and the counter electrode may be 0 V. When the reference electrode is included, Lt; / RTI >

In one embodiment of the present invention, the voltage may alternately be applied to the working electrode and the counter electrode, respectively, and may be applied to the working electrode and the counter electrode for about 1 second to about 50 seconds, respectively, It is not. For example, the time for which a voltage can be applied to each of the working electrode and the counter electrode is about 1 second to about 50 seconds, about 5 seconds to about 50 seconds, about 10 seconds to about 50 seconds, about 15 seconds to about From about 30 seconds to about 50 seconds, from about 20 seconds to about 50 seconds, from about 25 seconds to about 50 seconds, from about 30 seconds to about 50 seconds, from about 35 seconds to about 50 seconds, from about 40 seconds to about 50 seconds, From about 1 second to about 45 seconds, from about 1 second to about 40 seconds, from about 1 second to about 35 seconds, from about 1 second to about 30 seconds, from about 1 second to about 25 seconds, from about 1 second to about 20 seconds, From about 1 second to about 15 seconds, from about 1 second to about 10 seconds, or from about 1 second to about 5 seconds.

In one embodiment, the currents applied to the working electrode and the counter electrode, respectively, are in the range of about -2,000 mA / cm ² to about -1 mA / cm ² , and about 1 mA / cm ² to about 2,000 mA / ² , but is not limited thereto. For example, the current that can be applied to the working electrode is about -2,000 mA / cm ² to about -1 mA / cm ² , about -1,500 mA / cm ² to about -1 mA / cm ² , about -1,000 mA / cm ² and about -1 mA / cm ^2, from about -500 mA / cm ² and about -1 mA / cm ^2, from about -400 mA / cm ² and about -1 mA / cm ^2, from about -300 mA / cm ² and about -1 mA / cm ^2, from about -200 mA / cm ² and about -1 mA / cm ^2, from about -100 mA / cm ² and about -1 mA / cm ^2, from about -50 mA / cm ² to about -1 mA / cm ^2, from about -2,000 mA / cm ² to about -50 mA / cm ^2, from about -2,000 mA / cm ² to about -100 mA / cm ^2, from about -2,000 mA / cm ² to about - 200 mA / cm ^2, from about -2,000 mA / cm ² to about -300 mA / cm ^2, from about -2,000 mA / cm ² to about -400 mA / cm ^2, from about -2,000 mA / cm ² to about -500 mA / cm ² , about -2,000 mA / cm ² to about -1,000 mA / cm ² , or about -2,000 mA / cm ² to about -1,500 mA / cm ² . Also, the current that can be applied to the counter electrode is about 1 mA / cm ² to about 2,000 mA / cm ² , about 50 mA / cm ² to about 2,000 mA / cm ² , about 100 mA / cm ² to about 2,000 mA / cm ^2, about 200 mA / cm ² to about 2,000 mA / cm ^2, about 300 mA / cm ² to about 2,000 mA / cm ^2, about 400 mA / cm ² to about 2,000 mA / cm ^2, about 500 mA / cm ² to about 2,000 mA / cm ^2, from about 1,000 mA / cm ² to about 2,000 mA / cm ^2, from about 1,500 mA / cm ² to about 2,000 mA / cm ^2, about 1 mA / cm ² to about 1,500 mA / cm ^2, about 1 mA / cm ² to about 1,000 mA / cm ^2, about 1 mA / cm ² to about 500 mA / cm ^2, about 1 mA / cm ² to about 400 mA / cm ^2, about 1 mA / cm ² to about 300 mA / cm ^2, about 1 mA / cm ² to about 200 mA / cm ^2, about 1 mA / cm ² to about 100 mA / cm ^2, or about 1 mA / cm ² to about 50 mA / cm ² But is not limited thereto.

In one embodiment of the present invention, the magnitudes of the currents applied to the working electrode and the counter electrode may be different from each other. If the electrochemical reduction apparatus does not include the reference electrode, the reference current of the current applied to the working electrode and the counter electrode may be 0 mA / cm ^2. If the reference electrode is included, May be the current of the reference electrode.

In one embodiment of the present invention, the current may alternately be applied to the working electrode and the counter electrode, respectively, and may be applied to the working electrode and the counter electrode for about 1 second to about 50 seconds, respectively, It is not. For example, the time during which the current can be applied to each of the working electrode and the counter electrode is about 1 second to about 50 seconds, about 5 seconds to about 50 seconds, about 10 seconds to about 50 seconds, about 15 seconds to about From about 30 seconds to about 50 seconds, from about 20 seconds to about 50 seconds, from about 25 seconds to about 50 seconds, from about 30 seconds to about 50 seconds, from about 35 seconds to about 50 seconds, from about 40 seconds to about 50 seconds, From about 1 second to about 45 seconds, from about 1 second to about 40 seconds, from about 1 second to about 35 seconds, from about 1 second to about 30 seconds, from about 1 second to about 25 seconds, from about 1 second to about 20 seconds, From about 1 second to about 15 seconds, from about 1 second to about 10 seconds, or from about 1 second to about 5 seconds.

In one embodiment, the electrochemical reduction device for carbon dioxide and / or carbon monoxide may be a batch, circulation, continuous, polymer electrolyte membrane (PEM) type system, or combinations thereof And the like.

1, when the electrochemical reduction apparatus 101 for the carbon dioxide and / or carbon monoxide is a batch type, the reduction electrode unit 110 and / The oxidation electrode unit 120 may be separated. Each of the reducing electrode unit 110 and the oxidizing electrode unit 120 includes an electrolyte solution 190. The working electrode 140 and the oxidizing electrode unit 120 include the working electrode 140 and the counter electrode 150, Respectively. Carbon dioxide and / or reactant supplied from the first chamber 170 is supplied to the reduction electrode unit 110 and a carrier gas is selectively supplied to the oxidation electrode unit 120 from the second chamber 180, if necessary. Unlike the comparative device of FIG. 2, the two electrode units are connected to each other by a power supply unit 160, and the working electrode 140 (not shown) connected by the power supply unit 160, And the counter electrode 150, and / or the direction of the current are periodically switched with time. The unnecessary gas generated during the reaction is discharged through the gas outlet 200. The product produced by applying the voltage and current and the electrolyte solution containing the product and the electrolyte solution are collected after the reaction is continued for a predetermined time, and a new reaction can be performed by replacing with a new electrolyte solution.

3, when the electrochemical reduction apparatus 101 for the carbon dioxide and / or carbon monoxide is a circulating type, the carbon dioxide and / or the reactant and the electrolyte are continuously supplied from the first chamber 170 And the product produced by the electrolyte and the reduction reaction is supplied to the first product collecting chamber 210 through the discharge pipe located in the upper portion of the apparatus, . ≪ / RTI > At the same time or at a different point in time, the carrier gas and / or electrolyte is continuously supplied from the second chamber 180 to the oxidizing electrode portion 120 through the inlet pipe located at the lower portion of the apparatus, and the carrier gas and / The electrolyte may be continuously collected into the second product collection chamber 220 through a discharge line located at the top of the apparatus. The reduction electrode unit 110 includes a working electrode 140 and the oxidation electrode unit 120 includes a counter electrode 150. The two electrode units may be separated from each other by a membrane 130 . A plate 230 is positioned on the outer side of the two electrode units, and spacers 240 are disposed on the upper and lower sides of the plate 230, respectively. The working electrode 140 and the counter electrode 150 are connected to each other by a power supply unit 160. Unlike the comparative example apparatus of FIG. 4, the voltage and current are not constant, And / or the direction of the current applied to each of the working electrode and the counter electrode connected to each other by the switching unit (not shown) is periodically switched with time.

5, when the electrochemical reduction apparatus for carbon dioxide is a polymer electrolyte membrane (PEM) type system, carbon dioxide and / or reactant and electrolyte are continuously supplied from the first chamber And the product produced by the electrolyte and the reduction reaction is continuously collected into the first product collection chamber through the discharge pipe located at the top of the device have. At the same time or at a different point in time, the carrier gas and / or the electrolyte are continuously supplied from the second chamber to the oxidizing electrode portion through the inlet pipe located at the lower portion of the apparatus, and the carrier gas and / To the second product collection chamber through a discharge line located in the second product collection chamber. The reduction electrode unit may include a working electrode and the oxidation electrode unit may include a counter electrode. The mesh electrode may be attached to the working electrode and the counter electrode. The two electrode portions may be separated from each other by a membrane. A plate is positioned on the outer side of the two electrode portions, and a gasket spacer is disposed on the upper and lower portions, respectively. The mesh electrodes attached to the working electrode and the counter electrode are connected to each other by a power supply unit. Unlike the comparative example apparatus of FIG. 6, the voltage and current are not constant, The polarity of the voltage applied to each of the mesh electrode to which the electrode is attached and the mesh electrode to which the counter electrode is attached, and / or the direction of the current are periodically switched with time.

In one embodiment of the present invention, the electrochemical reduction apparatus for the carbon dioxide may be plural, and may be connected in series, parallel, or stacking structure, but is not limited thereto.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are given for the purpose of helping understanding of the present invention, but the present invention is not limited to the following Examples.

[ Example ]

Figs. 1 and 2 are schematic views showing an apparatus for electrochemical reduction of carbon dioxide and / or carbon monoxide in the present embodiment and an apparatus for electrochemical reduction of carbon dioxide and / or carbon monoxide in a comparative example, respectively. The results of Examples 1 to 5 and Comparative Examples 1 to 5, in which the directions and intensities of the applied voltage and the current were varied by using the carbon dioxide and / or carbon monoxide electrochemical reduction apparatuses of the examples and comparative examples, respectively, Respectively. The following Faraday efficiency was calculated using Equation (1) below, and the following energy conversion efficiency was calculated using Equation (2) below.

<Formula 1>

(ε _Faradaic : Faraday efficiency, Q: Charge flow, z: number of electrons exchanged, n: number of moles of product, F: Faraday constant)

<Formula 2>

(ε _energetic : energy conversion efficiency, E _eq : theoretical potential of the cell, E: actual driving potential of the cell, ε _Faradaic : Faraday efficiency, η: overvoltage)

< Comparative Example  1>

A reduction reaction of carbon dioxide and / or carbon monoxide was carried out under the following conditions:

Working electrode: Copper (Cu)

Counter electrode: Platinum (Pt)

Electrolyte: 0.5 M KHCO ₃

Pressure: 3.3 atm

Temperature: 10 ° C

Feeding rate of carbon dioxide: 200 mL / min

Working electrode: fixed voltage -4.65 V, fixed current -14.3 mA / cm ²

[Table 1]

The reactants in Comparative Example 1 were water and carbon dioxide, and the products produced were hydrogen, carbon monoxide, methane, ethanol, and n-propanol, and the molar ratio of hydrogen to carbon monoxide was 9.8, Containing product has a molar ratio of 3.1, a total number of electrons of 172, a total number of electrons of the carbon-containing product of 204, a ratio of the total number of hydrogen to the total number of carbon-containing products of 0.84, a Faraday efficiency of 54%, and The energy conversion efficiency was 24%.

< Example  1>

Example 1 was carried out under the same conditions as in Comparative Example 1 except for the voltage and current conditions applied to the counter electrode and the working electrode described below.

Counter electrode: 0.33 V / 1.8 mA / cm 2/3 cho

Working electrode: -4.7 V / -16.1 mA / cm 2/8 cho

[Table 2]

The reactants in Example 1 were water and carbon dioxide, and the resulting products were hydrogen, carbon monoxide, methane, ethylene, ethanol, and propanol, the molar ratio of hydrogen to carbon monoxide was 3.2, Containing product has a molar ratio of 0.9, a total number of electrons of 91.3, a total number of electrons of 494, a ratio of the total number of hydrogen to the total number of carbon-containing products of 0.18, a Faraday efficiency of 90%, and The energy conversion efficiency was 27%.

< Comparative Example  1 and Example  1 Results Analysis>

The molar ratio of hydrogen to the carbon-containing product was relatively high at 3.1, while the molar ratio of hydrogen to the carbon-containing product at Example 1 was relatively low at 0.9, which was lower than that of Comparative Example 1, Containing product was found to be high.

< Comparative Example  2>

A reduction reaction of carbon dioxide and / or carbon monoxide was carried out under the following conditions:

Working electrode: Copper (Cu)

Counter electrode: Platinum (Pt)

Electrolyte: 0.1 M KHCO ₃ and 0.1 M KOH

Pressure: 3.3 atm

Temperature: 10 ° C

Feeding rate of carbon dioxide: 200 mL / min

Working electrode: fixed voltage -3.9 V, fixed current -300 mA / cm ²

[Table 3]

The reactant in Comparative Example 2 was carbon dioxide, and as shown in Table 3, the products produced were hydrogen, carbon monoxide, and methane, the molar ratio of hydrogen to carbon monoxide was 13.6, the molar ratio of hydrogen to carbon- , The Faraday efficiency was 71%, and the energy conversion efficiency was 35%.

< Example  2>

Example 2 was carried out under the same conditions as in Comparative Example 2 except for the voltage and current conditions applied to the counter electrode and the working electrode described below.

Counter electrode: 1.8 V / 60 mA / cm 2 to 130 mA / cm ^2/3 cho

Working electrodes: -4 V / -350 mA / cm 2 to about -126 mA / cm ^2/15 cho

[Table 4]

The reaction products in Example 2 were water and carbon dioxide. As shown in Table 4, the produced products were hydrogen, carbon monoxide, ethylene, methane, ethanol, and n-propanol. The molar ratio of hydrogen to carbon monoxide was 2.3, The molar ratio of the large carbon-containing product was 0.3, the Faraday efficiency was 88%, and the energy conversion efficiency was 26%.

< Comparative Example  2 and Example  2 results analysis>

The molar ratio of hydrogen to the carbon-containing product was relatively high at 6.4, while the molar ratio of hydrogen to the carbon-containing product was very low at 0.3 as compared to Comparative Example 2, Containing product was found to be very high.

< Comparative Example  3>

A reduction reaction of carbon dioxide and / or carbon monoxide was carried out under the following conditions:

The ratio of working electrode: gold (Au), silver (Ag), copper (Cu) / 1: 1:

Counter electrode: Platinum (Pt)

Electrolyte: 0.5 M KHCO ₃

Pressure: 3.3 atm

Temperature: 10 ° C

Feeding rate of carbon dioxide: 200 mL / min

Working electrode: fixed voltage -4.7 V, fixed current -14.3 mA / cm ²

[Table 5]

As shown in Table 5, the produced products were hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide was 1.28, the Faraday efficiency was 100%, and the energy conversion efficiency was 28 %.

< Example  3>

Example 3 was carried out under the same conditions as in Comparative Example 3 except for the voltage and current conditions applied to the counter electrode and the working electrode described below.

Counter electrode: 1.0 V / 2 mA / cm 2/3 cho

Working electrode: -3.9 V / -12 mA / cm 2/8 cho

[Table 6]

As shown in Table 6, the produced products were hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide was 0.39, the Faraday efficiency was 91%, and the energy conversion efficiency was 50 %.

< Comparative Example  3 and Example  3 Results>

In Comparative Example 3, the molar ratio of hydrogen to carbon monoxide was comparatively high as 1.28, while in Example 3, the molar ratio of hydrogen to carbon monoxide was 0.39, which was relatively low, confirming that the molar ratio of carbon monoxide in the total product was higher than that of Comparative Example 3 I could.

< Comparative Example  4>

A reduction reaction of carbon dioxide and / or carbon monoxide was carried out under the following conditions:

Working Electrode: Gold (Au)

Counter electrode: Platinum (Pt)

Electrolyte: 0.5 M KHCO ₃

Pressure: 3.3 atm

Temperature: 10 ° C

Feeding rate of carbon dioxide: 200 mL / min

Working electrode: fixed voltage -6.4 V, fixed current -30.0 mA / cm ²

[Table 7]

As shown in Table 7, the produced products were hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide was 1.70, the Faraday efficiency was 100%, and the energy conversion efficiency was 20 %.

< Example  4>

Example 4 was carried out under the same conditions as in Comparative Example 4 except for the voltage and current conditions applied to the counter electrode and the working electrode described below.

Counter electrode: 3.63 V / 13 mA / cm 2/3 cho

Working electrodes: -5.82 V / -30 mA / cm 2/8 cho

[Table 8]

The reactants in Example 4 were water and carbon dioxide. As shown in Table 8, the produced products were hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide was 0.38, the Faraday efficiency was 91%, and the energy conversion efficiency was 21 %.

< Comparative Example  4 and Example  4 Analysis of Results>

In Comparative Example 4, the molar ratio of hydrogen to carbon monoxide was relatively high as 1.70, while in Example 4, the molar ratio of hydrogen to carbon monoxide was 0.38, which was relatively low, confirming that the molar ratio of carbon monoxide in the total product was higher than that of Comparative Example 4 I could.

< Comparative Example  5>

A reduction reaction of carbon dioxide and / or carbon monoxide was carried out under the following conditions:

Working electrode: silver (Ag)

Counter electrode: Platinum (Pt)

Electrolyte: 0.5 M KHCO ₃

Pressure: 3.3 atm

Temperature: 10 ° C

Feeding rate of carbon dioxide: 200 mL / min

Working electrode: fixed voltage -6.4 V, fixed current -30.0 mA / cm ²

[Table 9]

As shown in Table 9, the produced products were hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide was 6.70, the Faraday efficiency was 100%, and the energy conversion efficiency was 30 %.

< Example  5>

Example 5 was carried out under the same conditions as in Comparative Example 4 except for the voltage and current conditions applied to the counter electrode and the working electrode described below.

Counter electrode: 1.74 V / 12.5 mA / cm 2/3 cho

Working electrode: -4.5 V / -30.4 mA / cm 2/8 cho

[Table 10]

As shown in Table 10, the produced products were hydrogen and carbon monoxide, the molar ratio of hydrogen to carbon monoxide was 0.37, the Faraday efficiency was 89%, and the energy conversion efficiency was 26 %.

&Lt; Analysis of Results of Comparative Example 5 and Example 5 >

In the case of Comparative Example 5, the molar ratio of hydrogen to carbon monoxide was 6.70, which was relatively high. In Example 5, the molar ratio of hydrogen to carbon monoxide was very low as 0.37, and the molar ratio of carbon monoxide in the total product was very high I could confirm.

<Results Analysis of Comparative Examples 1 to 5 and Examples 1 to 5>

As shown in Comparative Examples 1 to 5 and Examples 1 to 5, the molar ratio of hydrogen in the products of Examples 1 to 5 according to the present invention was lower than those of Comparative Examples 1 to 5. This is consistent with FIG. 7, which shows that the amount of hydrogen in the overall composition of the product is small and that materials containing carbon other than hydrogen are produced as the main product.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention.

101: Electrochemical reduction device of carbon dioxide
110: reduction electrode part 190: electrolyte
120: oxidation electrode part 200: gas discharge port
130: Membrane 210: First product collection chamber
140: working electrode 220: second product collecting chamber
150: counter electrode 230: plate
160: Power supply unit 240: Spacer
170: first chamber 180: second chamber

Claims (18)

An oxidation electrode portion including a reduction electrode portion including a working electrode and a counter electrode;
A first chamber for supplying carbon dioxide and / or a reactant to the reduction electrode unit;
An optional second chamber for supplying carrier gas to the oxidation electrode portion if necessary; And
A power supply for applying a voltage and a current to the working electrode and the counter electrode, respectively,
/ RTI &gt;
Wherein a polarity of a voltage applied to each of the working electrode and the counter electrode, and / or a direction of the current is periodically switched,
An electrochemical reduction device for carbon dioxide and / or carbon monoxide.
The method according to claim 1,
Wherein the polarity and magnitude of the voltage applied to the working electrode and the counter electrode, respectively, and / or the direction and intensity of the current are periodically switched.
The method according to claim 1,
Wherein the working electrode and the counter electrode each independently comprise a material selected from the group consisting of a metal, an alloy, a nonmetal, an oxide, a sulfide, a phosphide, a nitride of the metal or an alloy, and combinations thereof. Electrochemical reduction device of carbon monoxide.
The method according to claim 1,
Further comprising a reference electrode located in the reducing electrode portion.
The method according to claim 1,
Wherein the reactants include those selected from the group consisting of water, carbon monoxide, chemical additives, and combinations thereof.
The method according to claim 1,
In the electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide, the product produced by the reduction reaction is selected from the group consisting of hydrogen, carbon monoxide, hydrocarbons, alcohols, aldehydes, organic acids, , An electrochemical reduction device for carbon dioxide and / or carbon monoxide.
The method according to claim 1,
Wherein the voltages applied to the working electrode and the counter electrode are respectively between -10 V and -1 V and between 0.5 V and 10 V. The electrochemical reduction apparatus for carbon dioxide and /
The method according to claim 1,
Wherein the currents applied to the working electrode and the counter electrode are respectively -2000 mA / cm ² to -1 mA / cm ² and 1 mA / cm ² to 2,000 mA / cm ² , .
The method according to claim 1,
The electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide may be a batch type, a circulation type, a continuous type, a polymer electrolyte membrane (PEM) type system, or a mixed type structure composed of combinations thereof Carbon dioxide and / or carbon monoxide.
An electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide comprising an electrode portion including a reducing electrode portion including a working electrode and a counter electrode
Supplying carbon dioxide and / or a reactant to the reduction electrode portion and selectively supplying a carrier gas to the oxidation electrode portion, and
And / or reducing the carbon dioxide and / or carbon monoxide supplied to the reduction electrode unit by periodically switching the polarity of the voltage applied to the working electrode and the counter electrode and / or the direction of the current
/ RTI &gt; and / or &lt; RTI ID = 0.0 &gt; carbon monoxide &lt; / RTI &gt;
11. The method of claim 10,
Wherein the polarity and magnitude of the voltage applied to the working electrode and the counter electrode, respectively, and / or the direction and intensity of the current are periodically switched.
11. The method of claim 10,
Wherein the working electrode and the counter electrode each independently comprise a material selected from the group consisting of a metal, an alloy, a nonmetal, an oxide, a sulfide, a phosphide, a nitride of the metal or an alloy, and combinations thereof. Method for electrochemical reduction of carbon monoxide.
11. The method of claim 10,
Wherein the reducing apparatus further comprises a reference electrode located in the reducing electrode section.
11. The method of claim 10,
Wherein the reactant comprises a material selected from the group consisting of water, carbon monoxide, chemical additives, and combinations thereof.
11. The method of claim 10,
Wherein the product produced by the reduction reaction of carbon dioxide and / or carbon monoxide comprises one selected from the group consisting of hydrogen, carbon monoxide, hydrocarbons, alcohols, aldehydes, organic acids, and combinations thereof. Method for electrochemical reduction of carbon monoxide.
11. The method of claim 10,
Wherein the voltages respectively applied to the working electrode and the counter electrode are -10 V to -1 V and 0.5 V to 10 V, respectively.
11. The method of claim 10,
Wherein the currents applied to the working electrode and the counter electrode are respectively -2,000 mA / cm ² to -1 mA / cm ² and 1 mA / cm ² to 2,000 mA / cm ² , respectively, in an electrochemical reduction method of carbon dioxide and / .
11. The method of claim 10,
The electrochemical reduction apparatus for carbon dioxide and / or carbon monoxide may be a carbon dioxide and / or carbon dioxide reforming apparatus having a mixed-type structure consisting of a batch system, a circulation system, a continuous system, a polyelectrolyte membrane system, Method for electrochemical reduction of carbon monoxide.

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