Carbon dioxide capture and release device

Abstract

This carbon dioxide capture and release device comprises: a composite containing a carbon-containing member and an anthraquinone derivative that is chemically bonded to the surface of the carbon-containing member; and an electrode having the composite at the surface.

Description

Carbon dioxide absorption and release device

[0001] The present disclosure relates to a carbon dioxide absorption and release device.

[0002] Carbon dioxide separation and capture has attracted attention as a technology for reducing the greenhouse gas carbon dioxide (CO2). Carbon dioxide separation and capture technology is mainly used to separate and capture carbon dioxide contained in exhaust gases from factories and in the atmosphere from other substances.

[0003] Carbon dioxide Capture and Utilization (CCU), which uses carbon dioxide to produce chemicals, fuels, etc., and Carbon dioxide Capture and Storage (CCS), which stores carbon dioxide deep underground, require the separation of carbon dioxide from other gases. The technology for capturing, utilizing, and storing carbon dioxide is called CCUS. Carbon dioxide separation and capture is a technology required to promote CCUS.

[0004] As an example of such a carbon dioxide separation and recovery technology, Non-Patent Document 1 discloses a carbon dioxide absorption and release device having a configuration in which a composite in which molecules exhibiting redox activity, such as polyanthraquinone or polyvinylferrocene, are bound to carbon nanotubes is provided on the surface of a non-woven carbon mat collector.

[0005] Furthermore, Patent Document 1 discloses a carbon dioxide absorption / release device including an electrode having a porous composite including a conductive member and a porous body on the conductive member, the porous body having angstrom-sized or nanometer-sized pores and including a molecular moiety that exhibits redox activity in response to electricity. The carbon dioxide absorption / release devices disclosed in Non-Patent Document 1 and Patent Document 1 have a porous composite film provided on the surface of the electrode. The porous composite physically fixes an anthraquinone derivative such as polyanthraquinone or anthraquinone to the surface of a conductive member such as carbon nanotubes using a binder or the like.

[0006] Japanese Patent Application Laid-Open No. 2023-033072

[0007] S. Voskian, TA Hatton, Energy Environ. Sci., 12, 3530 (2019)

[0008] One aspect of this embodiment is a carbon dioxide absorption / release device as follows: (1) A carbon dioxide absorption / release device comprising: a carbon-containing member and a composite containing an anthraquinone derivative chemically bonded to the surface of the carbon-containing member; and an electrode having the composite on its surface. (2) The carbon dioxide absorption / release device according to (1), in which the anthraquinone derivative is chemically bonded to the surface of the carbon-containing member via a linker. (3) The carbon dioxide absorption / release device according to (2), in which the linker is a diamine. (4) The carbon-containing member according to (1), in which the carbon-containing member is one or more types selected from the group consisting of graphene oxide, carbon nanotubes, activated carbon, ordered mesoporous carbon, and graphene mesosponge. (5) The carbon dioxide absorption / release device according to (1), in which the carbon-containing member has one or more shapes selected from the group consisting of a sheet, a thin plate, a stick, a fiber, a tube, and a flake. (6) The carbon dioxide absorption / release device according to (1), further comprising an electrolyte held in the composite. (7) The carbon dioxide absorption / release device according to any one of (1) to (6), wherein the electrode further comprises a current collector, the current collector containing one or more types of material selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel, and having one or more shapes selected from the group consisting of a sheet, a flake, a stick, a plate, and a mesh, and the composite is disposed on a surface of the current collector.

[0009] 1 is a schematic diagram of a carbon dioxide absorption / release device according to one aspect of the present embodiment; 2 is a schematic diagram showing an example of the structure of a composite according to one aspect of the present embodiment; 3 is a graph showing the CV measurement results according to Test Example 3; and 4 is a graph showing the CV measurement results according to Test Example 4.

[0010] Next, embodiments of the present disclosure will be described in detail with reference to the drawings. It should be understood that the present disclosure is not limited to the following embodiments, and that appropriate design changes, improvements, etc. may be made based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present disclosure.

[0011] (Configuration of Carbon Dioxide Absorption / Release Device) Fig. 1 shows a schematic diagram of a carbon dioxide absorption / release device 10 according to an embodiment of the present disclosure. The configuration shown in Fig. 1 is an example, and is not limited to this. In the carbon dioxide absorption / release device 10, a composite 11 is provided on the surface of an electrode 12. When the electrode 12 is in the shape of a plate as shown in Fig. 1, the composite 11 may be provided on both surfaces of the electrode 12, or on only one surface. The composite 11 may be provided on a part of the surface of the electrode 12, or on the entire surface of the electrode 12.

[0012] <Composite> The composite of the carbon dioxide absorption / release device according to this embodiment contains an anthraquinone derivative chemically bonded to the surface of a carbon-containing member. The anthraquinone derivative may be chemically bonded to the surface of the carbon-containing member via a linker. FIG. 2 schematically shows one embodiment of the structure of composite 11. In the embodiment shown in FIG. 2, composite 11 contains an anthraquinone derivative 14 chemically bonded to the surface of carbon-containing member 13 via a diamine as linker 15. According to this embodiment, by modifying the surface of the conductive member with the anthraquinone derivative by chemical bonding, the binding strength of the anthraquinone derivative to the surface of the conductive member can be increased compared to when the anthraquinone derivative is physically fixed as in Non-Patent Document 1 and Patent Document 1. As a result, the carbon dioxide absorption / release device according to this embodiment has high electronic conductivity and durability.

[0013] <Carbon-Containing Member> The carbon-containing member contained in the composite may contain a carbon material having good electrical conductivity. The carbon material may be one or more selected from the group consisting of graphene oxide, carbon nanotubes, activated carbon, regular mesoporous carbon, and graphene meso-sponge. The shape of the carbon-containing member is not particularly limited, and a shape suitable for the desired device configuration may be used. The carbon-containing member may have one or more shapes selected from the group consisting of, for example, a sheet, a thin plate, a stick, a fiber, a tube, and a flake. The carbon-containing member may be non-porous or porous.

[0014] Graphene oxide is a sheet-like or flake-like structure with a thickness of approximately 1 nm, which has numerous oxygen-containing functional groups, such as hydroxyl groups, carboxyl groups, carbonyl groups, and epoxy groups, on the surface of the single-layer graphene.

[0015] Graphene oxide has a sheet-like or flake-like structure and is highly flexible, which improves the flexibility of a composite using graphene oxide as a carbon-containing member.

[0016] As described above, the graphene oxide is not particularly limited as long as it is a sheet-like or flake-like structure having a thickness of about 1 nm and has a large number of oxygen-containing functional groups on the surface of the single-layer graphene. For example, reduced graphene oxide, modified graphene oxide, etc. can be used as the graphene oxide. Reduced graphene oxide is graphene oxide having functional groups in which some or all of the many oxygen-containing functional groups have been reduced. Modified graphene oxide is graphene oxide having functional groups in which some or all of the many oxygen-containing functional groups have been modified with desired functional groups.

[0017] Carbon nanotubes are carbon materials with many excellent properties, including high electrical conductivity, light weight, high strength, a large specific surface area, and flexibility. Carbon nanotubes are carbon-based materials formed by rolling graphene sheets into a cylindrical shape, and are classified as single-walled carbon nanotubes and multi-walled carbon nanotubes based on the number of walls. The use of single-walled carbon nanotubes increases the flexibility of the composite. On the other hand, the use of multi-walled carbon nanotubes increases the strength of the composite. Carbon nanotubes may have structures such as chiral (helical), zigzag, and armchair structures.

[0018] Activated carbon is a substance whose main component is carbon that has been subjected to chemical or physical treatment (activation / activation). The surface of activated carbon is highly porous, and the interior of its tiny holes (pores) is complexly developed. This structure allows activated carbon to adsorb many substances, mainly organic matter. The activated carbon contained in the composite can be processed into sheets, flakes, sticks, tubes, etc. for use.

[0019] Regular mesoporous carbon is a porous carbon with regular pores with diameters of 2 to 50 nm. The surface of regular mesoporous carbon is highly porous, and this structure allows it to adsorb many substances, primarily organic matter. In addition, regular mesoporous carbon has uniform pores and exhibits superior diffusion and molecular selectivity compared to activated carbon, which has non-uniform pore sizes, thereby further improving the functionality of carbon dioxide absorption / desorption devices. The regular mesoporous carbon contained in the composite can be processed into shapes such as sheets, flakes, sticks, and tubes for use.

[0020] Graphene meso sponge is a new carbon material developed by Tohoku University. It features a bubble-like pore structure of 3 to 8 nm and pore walls composed of a single, defect-free graphene sheet. Graphene meso sponge's precisely designed nanostructure achieves both excellent porosity and oxidation resistance, i.e., chemical durability, far exceeding that of conventional carbon materials. Furthermore, graphene meso sponge's flexibility allows it to be reversibly compressed and restored. This allows it to follow the movements of the active material, which undergoes drastic structural changes during charging and discharging, and it also has excellent mechanical durability.

[0021] <Anthraquinone Derivative> The anthraquinone derivative is chemically bonded to the surface of the carbon-containing member. The anthraquinone derivative may be chemically bonded to the surface of the carbon-containing member via a linker. For example, in the example shown in Figure 2, the anthraquinone derivative is bonded by substituting the Cl atom of anthraquinone acid chloride (anthraquinone-2-carbonyl chloride) shown in the following formula (1) for the N atom of the diamine linker.

[0022]

[0023] Anthraquinone derivatives are redox-active molecules, and as shown in the following formula (2), when an anthraquinone (skeleton) is reduced (E1) in the presence of carbon dioxide, carbon dioxide reacts with one of the oxygen atoms to produce carbonate. When it is further reduced (E'1), carbon dioxide reacts with the other oxygen atom to produce carbonate here as well. The reverse reaction is also possible, and the reduced anthraquinone (skeleton) is returned to its original anthraquinone (skeleton) state by repeated elimination of carbon dioxide and oxidation.

[0024]

[0025] When the anthraquinone derivative is chemically bonded to the surface of the carbon-containing member via a linker, the anthraquinone derivative may have a functional group bonded to a carbon atom of the benzene ring of the anthraquinone. The functional group reacts with the linker to bond to the linker, thereby allowing the anthraquinone derivative to chemically bond to the surface of the carbon-containing member via the linker. The anthraquinone derivative is not particularly limited as long as it can be chemically bonded to the surface of the carbon-containing member. In addition to the anthraquinone acid chloride described above, ethers containing an anthraquinone moiety, esters containing an anthraquinone moiety, etc. can be used as the anthraquinone derivative. An example of an ether containing an anthraquinone moiety is the compound shown in Formula (3) below. An example of an ester containing an anthraquinone moiety is the compound shown in Formula (4) below. In addition to these, halogen-substituted anthraquinone acid chlorides can also be used as anthraquinone derivatives. A halogen-substituted anthraquinone acid chloride is a compound in which a halogen, such as Cl or Br, is bonded to the benzene ring of the anthraquinone moiety, in addition to the acid chloride.

[0026]

[0027]

[0028] The linker is not particularly limited as long as it can chemically bond to the functional group of the benzene ring of the anthraquinone and simultaneously to the carbon atom of the conductive member, and examples thereof include linear carbon-chain diamines, phenylenediamines, etc. Furthermore, the number of carbon atoms in the diamine is not particularly limited, and linear carbon-chain diamines such as ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine (hexamethylenediamine) may be used. Linear carbon-chain diamines have high alkyl chain mobility, which makes it easier for the anthraquinone moiety to approach the carbon surface. In particular, ethylenediamine is a linear carbon-chain diamine with a short carbon chain, making it an extremely suitable linker for efficiently transferring electrons from redox-active molecules to the electrode surface.

[0029] The carbon dioxide absorption / release device according to this embodiment adsorbs and releases carbon dioxide to the anthraquinone (skeleton) by changing the potential applied to the device. That is, the carbon dioxide absorption / release device according to this embodiment performs gas adsorption / desorption using an electrochemical swing process in which a specific potential is maintained in the forward direction and a different potential is maintained in the reverse direction, repeatedly. In this process, affinity for the substance to be adsorbed (carbon dioxide) can be adjusted by using a redox-active molecule that can be oxidized at a predetermined potential and reduced at a different potential. The carbon dioxide absorption / release device according to this embodiment can absorb and release carbon dioxide at room temperature by using a complex that absorbs and releases carbon dioxide using a redox-active molecule having this configuration. Furthermore, because the anthraquinone derivative, which is a redox-active molecule, is chemically bonded to the surface of the carbon-containing material via a linker, it has good adhesion to the surface of the carbon-containing material.

[0030] <Electrode> The electrode of the carbon dioxide absorption and release device according to this embodiment may include a current collector having a composite on its surface. A known electrode material can be used for the current collector, and may include, for example, one or more materials selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel. The current collector may have one or more shapes selected from the group consisting of a sheet, a flake, a stick, a plate, and a mesh. The current collector may be porous.

[0031] The current collector functions as a conductor to transfer charge to the composite, causing the polyanthraquinone derivative to respond electrically. By changing the potential of the current collector, the polyanthraquinone derivative contained in the composite can be oxidized or reduced, causing the polyanthraquinone derivative to adsorb and release carbon dioxide.

[0032] The electrode of the carbon dioxide absorption / release device according to this embodiment may further include another carbon-containing member in addition to the carbon-containing member contained in the composite. By further including another carbon-containing member, electrical connection between the composites can be reinforced. Furthermore, when the electrode includes a current collector, electrical connection between the composite and the current collector can be reinforced. As with the carbon-containing member contained in the composite described above, graphene oxide, carbon nanotubes, activated carbon, ordered mesoporous carbon, graphene mesosponges, and the like can be used as such another carbon-containing member.

[0033] The carbon dioxide absorption / release device according to this embodiment may further include an electrolyte held in the composite. The component of the electrolyte is not particularly limited, but an ionically bonded salt, a solid electrolyte, or an ionically conductive polymer can be used. By including an electrolyte in the composite, the electrical conductivity is improved, and the carbon dioxide absorption / release capacity is enhanced.

[0034] The carbon dioxide absorption / release device according to this embodiment uses an electrode including the above-described composite as a working electrode, and applies a charge to the polyanthraquinone derivative of the composite by applying a potential to this working electrode. That is, by controlling the potential of the electrode, the redox state of the composite is switched between an oxidized state and a reduced state. The polyanthraquinone derivative can adsorb carbon dioxide in the reduced state and can release carbon dioxide in the oxidized state.

[0035] The carbon dioxide absorption / release device according to an embodiment of the present disclosure is a device that uses a composite that absorbs and releases carbon dioxide using an electrically responsive polyanthraquinone derivative, and can absorb and release carbon dioxide at room temperature. Therefore, it can be used in devices that capture carbon dioxide contained in factory exhaust gases, the atmosphere, and the like. Furthermore, carbon dioxide separation and capture technology is a pressing social issue, and the potential for industrial use of this device is extremely high.

[0036] (Method for Manufacturing Carbon Dioxide Absorption / Desorption Device) Next, as an example of a method for manufacturing a carbon dioxide absorption / desorption device according to this embodiment, a case in which chemical bonding is performed via a linker will be described. First, a suspension of a carbon-containing component is mixed with a solvent such as water. Next, an aqueous solution of a linker raw material such as ethylenediamine or hexamethylenediamine is added and ultrasonic agitation is performed. Next, after washing, the mixture is freeze-dried to produce a carbon-containing component having a linker bonded to its surface. Next, the carbon-containing component having a linker bonded to its surface is mixed with an organic solvent and agitated. Next, an anthraquinone derivative such as anthraquinone acid chloride is added and ultrasonic agitation is performed. Next, a base such as triethylamine is added, followed by heat treatment, washing, filtration, and vacuum drying to produce a composite containing an anthraquinone derivative chemically bonded to the surface of the carbon-containing component. Next, the obtained composite is applied to the surface of an electrode and heated and dried to form a composite on the surface of the electrode. In this manner, the carbon dioxide absorption / desorption device according to this embodiment can be manufactured.

[0037] (Method for separating and recovering carbon dioxide using a carbon dioxide absorption / release device) In the carbon dioxide absorption / release device according to this embodiment, carbon dioxide can be separated and recovered from a gas containing carbon dioxide by adsorbing carbon dioxide onto the composite, and the composite can be regenerated by desorbing carbon dioxide from the composite. Carbon dioxide can be adsorbed onto the composite by passing a current through the composite at the reduction potential of the composite, and contacting the composite with a gas containing carbon dioxide while maintaining the potential flowing through the composite at the reduction potential. Carbon dioxide can be desorbed from the composite and regenerated by switching the potential flowing through the composite that has adsorbed carbon dioxide to the oxidation potential of the composite. After carbon dioxide has been separated from the composite, the device can be set to the reduction potential again to perform the carbon dioxide adsorption process. In this way, by switching the potential of the current passed through the composite between the reduction potential and the oxidation potential, the device can be used repeatedly.

[0038] The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited thereto.

[0039] Test Example 1: Synthesis of graphene oxide with ethylenediamine bonded to the surface Graphene oxide with an oxidation degree of 55.0% by mass (manufactured by Nishina Materials Co., Ltd., product name: Rap eGO (TQ-11)-10) was prepared. Next, a graphene oxide suspension (3.05% by mass) was prepared, and 33 g of the graphene oxide suspension was added to a stirring vessel, followed by the addition of 300 g of water to prepare a mixed solution. Next, the mixed solution was stirred for 5 minutes using an ultra-high speed stirrer. Next, a mixed solution of 1 g of ethylenediamine and 200 g of water was added, followed by further stirring for 3 minutes using an ultra-high speed stirrer. Next, the mixed solution was washed three times by dialysis with water until the pH of the mixed solution reached approximately 8. Next, the mixture was freeze-dried for 48 hours to obtain 43.8 mg of graphene oxide with ethylenediamine as a linker bonded to the surface.

[0040] Test Example 2: Synthesis of a Composite in Which an Anthraquinone Derivative is Chemically Bonded to the Surface of Graphene Oxide via Ethylenediamine A 100-mL recovery flask was charged with 25.6 mg of graphene oxide having ethylenediamine bonded to its surface, as synthesized in Test Example 1, and 15 mL of N,N-dimethylformamide (DMF), followed by stirring. Next, 75 mg of anthraquinone-2-carbonyl chloride, represented by formula (1), was added, followed by ultrasonic stirring (40 kHz) for 15 minutes. Next, 200 μL of triethylamine was added, followed by heat treatment at 80°C for 24 hours, followed by reflux at 180°C for 24 hours. Next, washing with N,N-dimethylformamide (DMF) and filtration were performed three times. Next, washing with an aqueous sodium carbonate solution and filtration were performed three times. Next, washing with water and filtration were performed three times. Next, vacuum drying was performed for 48 hours, resulting in a composite containing an anthraquinone derivative chemically bonded to the surface of a carbon-containing member, as shown in FIG. 2. The structure of the complex was confirmed by X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR).

[0041] Test Example 3: CV measurement of carbon dioxide absorption / release device in the presence of Ar> 4.84 mg of the composite containing an anthraquinone derivative chemically bonded to the surface of the carbon-containing member produced in Test Example 2, 173.2 mg of isophorone, 20.0 mg of a 10% polyvinylidene fluoride (PVDF) solution (solvent: N-methyl-2-pyrrolidone:isophorone = 3:7 weight ratio), and 1.93 mg of acetylene black were placed in a microtube and subjected to ultrasonic treatment. 10 μL of the solution was then sampled and dropped onto the surface of a glassy carbon electrode, and dried at 80° C. overnight to produce a device sample. Next, a 1 M solution of 1-butyl, 1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMPTFSI) in dimethyl sulfoxide (DMSO) was prepared for the device sample. The electrode was immersed in the solution, and the current flow was measured by repeatedly switching the potential between -1.8 V and 0.3 V relative to a silver-silver chloride reference electrode at a scan rate of 10 mV / s. The experiment was performed in the absence of CO2 by bubbling argon gas through the electrolyte beforehand. By applying a voltage to the device sample in this manner, the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV) measurements. A BioLogic SP50-e was used for the CV measurements. The CV measurement results are shown in Figure 3. As shown in Figure 3, the cyclic voltammogram is expressed as a current-voltage curve. The current is considered to be a response signal to the potential excitation signal. Since Test Example 3 was carried out in the presence of Ar, the anthraquinone (skeleton) of the complex was reduced in two stages, with reduction peaks observed in the region E1 corresponding to the first reduction potential and in the region E2 corresponding to the second reduction potential, which was distant from the region E1. In the reverse reaction, oxidation also occurred in two stages, with oxidation peaks observed in the region E1 and in the region E2 distant from the region E1.

[0042] Test Example 4: CV Measurement of Carbon Dioxide Absorption / Desorption Device in the Presence of CO2 A similar device sample was prepared using the same procedure as in Test Example 3. Next, a dimethyl sulfoxide (DMSO) solution (1 M) of 1-butyl, 1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (BMPTFSI) was prepared for the device sample. The electrode was immersed in the solution, and the current flow was measured by repeatedly switching the potential between -1.8 V and 0.3 V relative to a silver-silver chloride reference electrode at a scan rate of 10 mV / s. In the experiment, the electrolyte was bubbled with argon gas beforehand, followed by CV measurement. Further CV measurement was performed in the presence of carbon dioxide (CO2) by bubbling CO2 gas. In this way, a voltage was applied to the device sample, and the electrochemical behavior of the composite was evaluated by cyclic voltammetry (CV). A BioLogic SP50-e was used for the CV measurement. The CV measurement results are shown in Figure 4. As shown in Figure 4, a cyclic voltammogram is expressed as a current-voltage curve. The current is considered to be a response signal to the potential excitation signal. Test Example 4 was performed in the presence of CO2, so the anthraquinone (skeleton) of the composite was reduced in one step, with the E1 and E2 regions overlapping each other, resulting in a single reduction peak. Furthermore, in the reverse reaction, oxidation occurred in one step, with the E1 and E2 regions overlapping each other, resulting in a single oxidation peak. As shown in Figure 4, when the anthraquinone (skeleton) is reduced in the presence of carbon dioxide (E1), carbon dioxide reacts with one of the oxygen atoms to produce carbonate. When it is further reduced (E'1), carbon dioxide reacts with the other oxygen atom to produce carbonate. The reverse reaction is also possible, and repeated desorption and oxidation of carbon dioxide returns the anthraquinone (skeleton) to its original state.

[0043] 10 Carbon dioxide absorption / release device 11 Composite 12 Electrode 13 Carbon-containing member 14 Anthraquinone derivative 15 Linker

Claims

1. A carbon dioxide absorption / release device comprising: a carbon-containing member; a composite containing an anthraquinone derivative chemically bonded to a surface of the carbon-containing member; and an electrode having the composite on a surface thereof.

2. The carbon dioxide absorption and release device according to claim 1, wherein the anthraquinone derivative is chemically bonded to the surface of the carbon-containing member via a linker.

3. The carbon dioxide absorbing and releasing device according to claim 2, wherein the linker is a diamine.

4. The carbon dioxide absorption and release device according to claim 1, wherein the carbon-containing member is one or more selected from the group consisting of graphene oxide, carbon nanotubes, activated carbon, ordered mesoporous carbon, and graphene meso sponge.

5. The carbon dioxide absorption and release device according to claim 1, wherein the carbon-containing member has one or more shapes selected from the group consisting of a sheet, a thin piece, a stick, a fiber, a tube, and a flake.

6. The carbon dioxide absorption and release device according to claim 1, further comprising an electrolyte retained in the composite.

7. The carbon dioxide absorption and release device according to any one of claims 1 to 6, wherein the electrode further includes a current collector, the current collector including one or more types selected from the group consisting of carbon, aluminum, copper, stainless steel, and nickel, and having one or more types of shapes selected from the group consisting of a sheet, a flake, a stick, a plate, and a mesh, and the composite is provided on a surface of the current collector.