KR20210158059A - Apparatus of generating hydrogen peroxide using two electron oxygen reduction reaction - Google Patents

Abstract

The present invention provides a hydrogen peroxide generator for generating hydrogen peroxide using a two-electron oxygen reduction reaction, which is an economical and simple facility as the hydrogen peroxide generator does not require an external power source and does not use noble metals such as palladium. The hydrogen peroxide generator according to an embodiment of the present invention includes: an anode; a cathode which is disposed to face the anode and is supplied with oxygen; an electrolyte disposed between the anode and the cathode and including water; and a catalyst body disposed on the cathode and generating hydrogen peroxide by making the oxygen react with the water by the two-electron oxygen reduction reaction.

Description

Apparatus of generating hydrogen peroxide using two electron oxygen reduction reaction

The technical idea of the present invention relates to a hydrogen peroxide generator, and more particularly, to a hydrogen peroxide generator using a two-electron oxygen reduction reaction.

Hydrogen peroxide has a strong oxidizing power and is used in various industries such as disinfectant, oxidizing agent, bleaching agent, catalyst, chemical synthesis, water treatment, pulp and paper manufacturing, and the like. In addition, hydrogen peroxide can replace chlorine due to its eco-friendly properties, and can be used in fields requiring generation and supply of oxygen. Conventional production of hydrogen peroxide mostly uses anthraquinone oxidation, and the method has high energy consumption and high device cost, such as using palladium (Pd) metal, which is a noble metal. In addition, in the conventional production of hydrogen peroxide, an electrochemical oxygen reduction reaction is used, but there is a limitation that an external power supply is essential for this reaction.

Korean Patent Registration No. 10-1966784

The technical problem to be achieved by the technical idea of the present invention is to provide a hydrogen peroxide generator that generates hydrogen peroxide using a two-electron oxygen reduction reaction as an economical and simple facility by not requiring an external power source and not using a noble metal such as palladium will provide

However, these tasks are exemplary, and the technical spirit of the present invention is not limited thereto.

A device for generating hydrogen peroxide according to the technical idea of the present invention for achieving the above technical problem is an anode; a cathode disposed to face the anode and supplied with oxygen; an electrolyte disposed between the anode and the cathode and comprising water; and a catalyst that is disposed on the cathode and causes a two-electron oxygen reduction reaction of the oxygen and the water to generate hydrogen peroxide, wherein one side of the cathode is in contact with the electrolyte, and the other side of the cathode is air or oxygen gas exposed in direct contact with

In one embodiment of the present invention, the oxygen supplied to the cathode may be provided using the air or the oxygen gas in direct contact with the cathode.

In an embodiment of the present invention, the electrolyte may transfer hydroxide ions (OH ⁻ ) between the anode and the cathode.

In one embodiment of the present invention, the hydrogen peroxide may be dissolved in the electrolyte in an ionic state.

In one embodiment of the present invention, the hydrogen peroxide generator, when generating the hydrogen peroxide, electrons move from the anode to the cathode, and thus may generate power.

In one embodiment of the present invention, the material constituting the anode is oxidized while the hydrogen peroxide is generated, and the oxidized material is reduced by charging to supplement the anode.

In one embodiment of the present invention, the catalyst body, the number of electrons participating in the oxygen reduction reaction calculated from the following formula may include a material in the range of 2 to 4.

n = 4 x I _d / (I _d + I _r /N)

(Where n is the number of electrons participating in the oxygen reduction reaction, I _d is the amount of current of the disk electrode, I _r is the amount of current of the ring electrode, and N is the collection efficiency of 0.41)

In an embodiment of the present invention, the catalyst body may include at least one of a metal, a metal alloy, a carbon compound, an oxide, and a perovskite material.

In one embodiment of the present invention, the catalyst body is platinum (Pt), cobalt (Co), nickel (Ni), manganese (Mn), copper (Cu), Pt-Hg alloy, Pd-Hg alloy, Ag It may include at least one of -Hg alloys.

In one embodiment of the present invention, the catalyst may include at least one of a carbon compound having a functional group and a carbon compound substituted with a hetero atom.

In one embodiment of the present invention, the anode may contain a material that loses electrons to become a cation.

In an embodiment of the present invention, the anode includes zinc (Zn), vanadium (V) chromium (Cr) manganese (Mn) iron (Fe) cobalt (Co) nickel (Ni) copper (Cu) aluminum (Al) , magnesium (Mg), and may include at least one of calcium (Ca).

A device for generating hydrogen peroxide according to the technical idea of the present invention for achieving the above technical problem is an anode; a cathode disposed facing the anode and supplied with oxygen; an electrolyte disposed between the anode and the cathode and comprising water; and a catalyst that is disposed on the cathode and causes a two-electron oxygen reduction reaction between the oxygen and the water to generate hydrogen peroxide, wherein the cathode is immersed in the electrolyte.

In one embodiment of the present invention, it is disposed adjacent to the cathode and may further include a gas injection unit for injecting air or oxygen gas into the electrolyte, wherein the oxygen supplied to the cathode is supplied to the cathode by the gas injection unit. It may be provided using the injected air or oxygen gas.

In one embodiment of the present invention, the oxygen supplied to the cathode may be provided using residual oxygen included in the electrolyte.

A device for generating hydrogen peroxide according to the technical idea of the present invention for achieving the above technical problem is an anode; a cathode disposed facing the anode and supplied with oxygen; an electrolyte disposed between the anode and the cathode and comprising water; and a catalyst that is disposed on the cathode and generates hydrogen peroxide by reacting the oxygen and the water with a two-electron oxygen reduction reaction.

Since the hydrogen peroxide generator according to the technical idea of the present invention can generate hydrogen peroxide using a two-electron oxygen reduction reaction, it does not require an additional device such as an external power source, and is an economical and simple device by not using a noble metal such as palladium. can be implemented as In addition, the hydrogen peroxide generator can produce electric power as a by-product along with the hydrogen peroxide generation, thereby increasing energy consumption efficiency, and also reducing the consumption of raw materials and increasing the lifespan of the device because the consumed anode can be replenished by charging. can do it

The above-described effects of the present invention have been described by way of example, and the scope of the present invention is not limited by these effects.

1 is a schematic diagram showing an apparatus for generating hydrogen peroxide according to an embodiment of the present invention.
2 is a schematic diagram showing an apparatus for generating hydrogen peroxide according to an embodiment of the present invention.
3 is a schematic diagram showing a rotating ring-disc electrode for determining the oxygen reduction reaction of the catalyst applied to the hydrogen peroxide generator according to an embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. The embodiments of the present invention are provided to more completely explain the technical idea of the present invention to those of ordinary skill in the art, and the following examples may be modified in various other forms, The scope of the technical idea is not limited to the following examples. Rather, these embodiments are provided so as to more fully and complete the present disclosure, and to fully convey the technical spirit of the present invention to those skilled in the art. In this specification, the same reference numerals refer to the same elements throughout. Furthermore, various elements and regions in the drawings are schematically drawn. Accordingly, the technical spirit of the present invention is not limited by the relative size or spacing drawn in the accompanying drawings.

1 is a schematic diagram showing a hydrogen peroxide generator 100 according to an embodiment of the present invention.

Referring to FIG. 1 , the hydrogen peroxide generator 100 includes an anode 110 , a cathode 120 , an electrolyte 130 disposed between the anode 110 and the cathode 120 , and a catalyst body 140 . .

The anode 110 may include a material that loses electrons to become a cation, and may include, for example, a metal. The anode 110 is, for example, zinc (Zn), vanadium (V) chromium (Cr) manganese (Mn) iron (Fe) cobalt (Co) nickel (Ni) copper (Cu) aluminum (Al), magnesium (Mg) ), and may include at least one of calcium (Ca). However, these materials are exemplary and the technical spirit of the present invention is not limited thereto. The anode 110 may have an arrangement in which one side is in contact with the electrolyte 130 , or may be immersed in the electrolyte 130 as shown in FIG. 2 below.

The cathode 120 may be disposed to face the anode 110 . One side of the cathode 120 may be in contact with the electrolyte 130 , and the other side of the cathode 120 may be exposed to be in direct contact with air or oxygen gas. Oxygen may be supplied to the cathode 120 as a raw material for generating the hydrogen peroxide. The supply of oxygen may be performed in various ways. For example, the oxygen supplied to the cathode 120 may be provided using the air or the oxygen gas in direct contact with the cathode 120 . In addition, the oxygen supplied to the cathode 120 may be provided using residual oxygen included in the electrolyte 130 .

A catalyst body 140 may be disposed on the cathode 120 . The cathode 120 may be made of a conductive material such as metal or carbon. The cathode 120 may include, for example, carbon paper or a nickel mesh. However, these materials are exemplary and the technical spirit of the present invention is not limited thereto.

In the hydrogen peroxide generator 100, since the cathode 120 can use oxygen in the air, theoretically, the weight of the cathode 120 can be reduced to zero or drastically. Therefore, since the weight of the anode 110 can be increased as the weight of the cathode 120 is reduced, the weight ratio of the anode 110 to the total weight of the hydrogen peroxide generator 100 is increased, as a result, the weight sugar can provide a high rate of hydrogen peroxide generation.

The electrolyte 130 may be disposed between the anode 110 and the cathode 120 . The electrolyte 130 may include an electrolytic material and may include water. The electrolyte 130 may transfer hydroxide ions (OH ⁻ ) between the anode 110 and the cathode 120 , and may include various materials performing this function. The electrolyte 130 may be, for example, a liquid material or a solid material. The electrolyte 130 may be, for example, an acidic material or a basic material. In the case where the electrolyte 130 has acidity, the synthesis efficiency of the hydrogen peroxide at room temperature may be higher than when the electrolyte 130 has basicity. For example, the electrolyte 130 may be composed of 1M to 6M KOH in the case of a strong basic solution, KHCO _{3 as a neutral solution, and HClO 4} or H ₂ SO as an acidic solution. ₄ may be included. However, these materials are exemplary and the technical spirit of the present invention is not limited thereto.

The catalyst body 140 may be disposed on the cathode 120 . The catalyst body 140 may generate hydrogen peroxide through a two-electron oxygen reduction reaction between oxygen and water, and may include a material that performs this function. The catalyst body 140 may include, for example, at least one of a metal, a metal alloy, a carbon compound, an oxide, and a perovskite material. The catalyst body 140 may include, for example, at least one of platinum (Pt), cobalt (Co), nickel (Ni), manganese (Mn), and copper (Cu) as a metal material dispersed in atomic units. can The catalyst body 140 may include, for example, at least one of a Pt-Hg alloy, a Pd-Hg alloy, and an Ag-Hg alloy. The catalyst 140 may include a carbon compound including a functional group, for example, a carbon compound including a carboxyl (-COOH) functional group or a carbon compound including an ether (C-O-C) functional group. In addition, the catalyst 140 may include a carbon compound in which a hetero atom is substituted. However, these materials are exemplary and the technical spirit of the present invention is not limited thereto.

Hereinafter, a hydrogen peroxide generation reaction in the hydrogen peroxide generator 100 will be described. In the anode 110 and the cathode 120, the reaction is as follows. Note that zinc is exemplarily selected as a material constituting the anode 110 in the following reaction scheme.

<Hydrogen Peroxide Generation Reaction Formula>

Anode Reaction: Zn + 2OH ^- -> ZnO + H ₂ O + 2e ^- (E ⁰ = -1.33 V vs. SHE)

Cathodic reaction: O ₂ + H ₂ O + 2e ^- -> HO ₂ ^- + OH ^- (E ⁰ = -0.065 V vs. SHE)

^{Hydroxide ions (OH −} ) formed in the cathode 120 pass through the electrolyte 130 and move to the anode 110 . The hydroxide ions (OH ⁻ ) react with the metal (M) constituting the anode to form a metal oxide (MO), water (H ₂ O), and electrons (2e ⁻ ). For example, when the metal is zinc (Zn), zinc oxide (ZnO) is formed. The generated electrons 2e ⁻ are supplied to the cathode 120 through the wiring 180 . In the cathode 120 , oxygen (O ₂ ), water (H ₂ O), and electrons (2e ⁻ ) react to form hydrogen peroxide (HO ₂ ⁻ ) and hydroxide ions (OH ⁻ ). The hydrogen peroxide (HO ₂ ⁻ ) may be dissolved in the electrolyte 130 in the form of ions, and then may be extracted as _{hydrogen peroxide (H 2} O _{2 ) from the electrolyte 130 .}

The hydrogen peroxide generator 100 may generate electric power by using a reaction between metal and oxygen. When the hydrogen peroxide generator 100 generates the hydrogen peroxide, electrons move from the anode 110 to the cathode 120 , thereby generating electric power. The power generated in this way may be provided to the load 190 . When the anode 110 is zinc, the spontaneously generated electromotive force becomes 1.27V. At this time, since the current flow passing through the load 190 is directed from the cathode 120 to the anode 110 , the cathode 120 becomes a + pole, and the anode 110 becomes a - pole. The advantage of such power generation is that it uses oxygen, which is infinitely present in nature, as an active material, has a very high theoretical energy density compared to other secondary batteries, and can also have friendly properties. In addition, since the hydrogen peroxide generator 100 does not contain a chemical oxidizing agent therein, there is no risk of explosion or fire, and the weight can be greatly reduced. In addition, compared to a fuel cell using hydrogen or alcohol, it is very economical, has excellent stability, and has excellent operating ability at a low temperature.

In addition, in the hydrogen peroxide generator 100 , the metal material of the anode 110 consumed through the charging process may be supplemented from the electrolyte 130 . The reaction formula at the time of charging is as follows.

<Reaction formula during charging>

Anode reaction: Zn(OH) ₄ ^2- + 2e ^- -> Zn + 4 OH ^- (aq)

Cathodic reaction: 4 OH ^- (aq) -> O ₂ (g)+ 2H ₂ O + 4e ^-

In the hydrogen peroxide generator 100, while the hydrogen peroxide is generated, the material constituting the anode 110 is oxidized to form an oxide or dissolved as ions in the electrolyte 130, and as a result, the anode 110 is consumed. By the charging as described above, the oxidized material may be reduced to supplement the consumed anode 110 . During the charging, electrons must be moved by connecting the anode 110 to the + pole of an external power source (not shown) and the cathode to the - pole of the external power source.

2 is a schematic diagram showing a hydrogen peroxide generator 200 according to an embodiment of the present invention. Descriptions of the same or similar components as those of the embodiment of FIG. 1 will be omitted.

Referring to FIG. 2 , the hydrogen peroxide generator 200 includes an anode 210 , a cathode 220 , an electrolyte 230 disposed between the anode 210 and the cathode 220 , and a catalyst body 240 . .

The cathode 220 may be disposed to face the anode 210, and oxygen may be supplied. The electrolyte 230 may be disposed between the anode 210 and the cathode 220 and may include water. The catalyst body 240 may be disposed on the cathode 220 , and may generate hydrogen peroxide by reacting the oxygen and the water with a two-electron oxygen reduction reaction.

The cathode 220 may be immersed in the electrolyte 230 . In addition, the anode 210 may be immersed in the electrolyte 230 , or may have an arrangement in which one side of the anode 210 contacts the electrolyte 230 as shown in FIG. 1 .

Oxygen may be supplied to the cathode 220 as a raw material for generating the hydrogen peroxide. The supply of oxygen may be performed in various ways.

The hydrogen peroxide generator 200 may further include a gas injection unit 270 . The gas injection unit 270 is disposed adjacent to the cathode 220 , and may inject air or oxygen gas into the electrolyte 230 . In this case, the oxygen to the cathode 220 may be provided using the air or oxygen gas injected by the gas injection unit 270 .

In addition, the oxygen supplied to the cathode 220 may be provided using residual oxygen included in the electrolyte 230 .

The wiring 280 of FIG. 2 may correspond to the wiring 180 of FIG. 1 . The load 290 of FIG. 2 may correspond to the load 190 of FIG. 1 .

The hydrogen peroxide generator according to the technical idea of the present invention generates hydrogen peroxide using a two-electron oxygen reduction reaction. Hereinafter, the two-electron oxygen reduction reaction will be described in detail.

Oxygen is reduced by an oxygen reduction reaction (ORR) to form water (H ₂ O), hydroxide ions (OH ^- ), hydrogen peroxide (H ₂ O ₂ ), and hydrogen peroxide radicals (HO ₂ ^- ) have. Hydrogen peroxide (HO ₂ ⁻ ) is a hydrogen peroxide anion (or radical) in a precise sense, but will be referred to as hydrogen peroxide in the present specification.

This oxygen reduction reaction can form different products depending on the number of participating electrons. A four-electron reaction formula in which four electrons participate in the oxygen reduction reaction and a two-electron reaction formula in which two electrons participate in the oxygen reduction reaction are shown below.

<4 electron reaction formula>

O ₂ + 2H ₂ O + 4e ^- <-> 4OH ^-

<2 electron reaction formula>

O ₂ + H ₂ O + 2e ^- <-> HO ₂ ^- + OH ^-

In the four-electron reaction equation, one oxygen (O ₂ ), two water (H ₂ O), and four electrons (e ⁻ ) react to form four hydroxide ions (OH ^{− ).} On the other hand, in the two-electron reaction formula, one oxygen (O ₂ ), one water (H ₂ O), and two electrons (e ^- ) react, and one hydrogen peroxide (HO ₂ ^- ) and one hydroxide ion ( OH ^- ). That is, in the two-electron reaction, hydrogen peroxide (HO ₂ ⁻ ) is formed as an intermediate product.

Depending on the type of catalyst in which the oxygen reduction reaction occurs, a four-electron reaction or a two-electron reaction dominates. As such, whether the generated oxygen reduction reaction is a four-electron reaction or a two-electron reaction can be determined using a rotating ring disk electrode (RRDE).

3 is a schematic diagram showing a rotating ring-disc electrode for determining the oxygen reduction reaction of the catalyst applied to the hydrogen peroxide generator according to an embodiment of the present invention.

Referring to FIG. 3 , the oxygen reduction reaction of the two-electron reaction occurring in the rotating ring-disk electrode is illustrated by way of example. The rotating ring-disk electrode includes a disk electrode 10 , a ring electrode 20 , and a catalyst 30 . When the catalyst 30 is disposed on the disk electrode 10 and electricity is applied, oxygen molecules receive two electrons and are reduced to change into hydrogen peroxide radicals and hydroxide ions, and again in the ring electrode 20, the hydrogen peroxide radicals and the The hydroxide ions are oxidized to transfer two electrons to the ring electrode 20 and are converted into oxygen molecules. As for the polarity of the applied electricity, the ring electrode 20 is a + pole and the disk electrode 10 is a - pole. The number of electrons participating in the oxygen reduction reaction can be calculated by the following formula.

<Electron count calculation formula>

n = 4 x I _d / (I _d + I _r /N)

(Where n is the number of electrons participating in the oxygen reduction reaction, I _d is the amount of current of the disk electrode, I _r is the amount of current of the ring electrode, and N is the collection efficiency of 0.41)

In order to generate hydrogen peroxide, the number (n) of electrons participating in the oxygen reduction reaction of the catalyst may be in the range of 2 to 4. The number of electrons is calculated by calculating the average value of the electrons used. The closer the number of electrons to two, the greater the two-electron reaction tendency, which means that the hydrogen peroxide production efficiency is increased accordingly. On the other hand, the closer the number of electrons to 4, the greater the tendency of the 4-electron reaction, which means that the hydrogen peroxide production efficiency is reduced accordingly. Accordingly, the catalyst may include a material in which the number of electrons participating in the oxygen reduction reaction calculated from the above formula is in the range of 2 to 4. Preferably, the catalyst body may include a material in which the number of electrons is in the range of 2 or more to less than 4.

In addition, the production degree of hydrogen peroxide generated in the hydrogen peroxide generator is as follows.

<Calculation formula for production of hydrogen peroxide>

[HO ₂ ^- ] (%) = 200 x (I _r /N) /(I _d + I _r /N)

(Here, I _d is the amount of current of the disk electrode, I _r is the amount of current of the ring electrode, and N is the collection efficiency of 0.41)

The collection efficiency (N) is a measure indicating the degree to which the product produced by the disk electrode is collected by the ring electrode, and may generally be 0.41.

The technical spirit of the present invention described above is not limited to the above-described embodiments and the accompanying drawings, and it is the technical spirit of the present invention that various substitutions, modifications and changes are possible without departing from the technical spirit of the present invention. It will be apparent to those of ordinary skill in the art to which this belongs.

100, 200: hydrogen peroxide generator
110, 210: anode, 120, 220: cathode,
130, 230: electrolyte, 140, 240: catalyst,
270: gas injection unit;
180, 280: wiring, 190, 290: load,
10: disk electrode, 20: ring electrode, 30: catalyst

Claims (16)

anode;
a cathode disposed facing the anode and supplied with oxygen;
an electrolyte disposed between the anode and the cathode and comprising water; and
A catalyst body disposed on the cathode and generating hydrogen peroxide by reacting the oxygen and the water with a two-electron oxygen reduction reaction;
One side of the cathode is in contact with the electrolyte, and the other side of the cathode is exposed to be in direct contact with air or oxygen gas, a hydrogen peroxide generator. The method according to claim 1,
The oxygen supplied to the cathode is provided using the air or the oxygen gas in direct contact with the cathode, a hydrogen peroxide generator. The method according to claim 1,
The electrolyte transfers hydroxide ions (OH ⁻ ) between the anode and the cathode, a hydrogen peroxide generator. The method according to claim 1,
The hydrogen peroxide is dissolved in the electrolyte in an ionic state, a hydrogen peroxide generator. The method according to claim 1,
In the hydrogen peroxide generator, when generating the hydrogen peroxide, electrons move from the anode to the cathode, thereby generating electric power. The method according to claim 1,
A material constituting the anode is oxidized while the hydrogen peroxide is generated, and the oxidized material is reduced by charging to supplement the anode. The method according to claim 1,
The catalyst body, the hydrogen peroxide generator comprising a material in which the number of electrons participating in the oxygen reduction reaction calculated from the following formula is in the range of 2 to 4.
n = 4 x I _d / (I _d + I _r /N)
(Where n is the number of electrons participating in the oxygen reduction reaction, I _d is the amount of current of the disk electrode, I _r is the amount of current of the ring electrode, and N is the collection efficiency of 0.41) The method according to claim 1,
The catalyst body, a hydrogen peroxide generator comprising at least one of a metal, a metal alloy, a carbon compound, an oxide, and a perovskite material. The method according to claim 1,
The catalyst includes at least one of platinum (Pt), cobalt (Co), nickel (Ni), manganese (Mn), copper (Cu), a Pt-Hg alloy, a Pd-Hg alloy, and an Ag-Hg alloy which is a hydrogen peroxide generator. The method according to claim 1,
The catalyst body includes at least one of a carbon compound containing a functional group and a carbon compound substituted with a hetero atom, a hydrogen peroxide generator. The method according to claim 1,
The anode contains a material that loses electrons and becomes a cation, a hydrogen peroxide generator. The method according to claim 1,
The anode is zinc (Zn), vanadium (V) chromium (Cr) manganese (Mn) iron (Fe) cobalt (Co) nickel (Ni) copper (Cu) aluminum (Al), magnesium (Mg), and calcium ( Ca) comprising at least one of, hydrogen peroxide generator. anode;
a cathode disposed facing the anode and supplied with oxygen;
an electrolyte disposed between the anode and the cathode and comprising water; and
a catalyst body disposed on the cathode and generating hydrogen peroxide by reacting the oxygen and the water with a two-electron oxygen reduction reaction;
The cathode is immersed in the electrolyte, hydrogen peroxide generator. 14. The method of claim 13,
It is disposed adjacent to the cathode, further comprising a gas injection unit for injecting air or oxygen gas into the electrolyte,
The oxygen supplied to the cathode is provided using the air or oxygen gas injected by the gas injection unit, a hydrogen peroxide generator. 14. The method of claim 13,
The oxygen supplied to the cathode is provided using residual oxygen contained in the electrolyte, a hydrogen peroxide generator. anode;
a cathode disposed facing the anode and supplied with oxygen;
an electrolyte disposed between the anode and the cathode and comprising water; and
A catalyst body disposed on the cathode and generating hydrogen peroxide by reacting the oxygen and the water with a two-electron oxygen reduction reaction.

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