KR102427852B1 - Carbon dioxide Reduction Catalyst using Graphitic Frustrated Lewis Pair and Carbon dioxide Reduction Battery System in Seawater using the same - Google Patents

Abstract

The present invention relates to a carbon dioxide reduction battery system in seawater using a graffiti incomplete Lewis acid-base pair catalyst. It relates to a battery system that can prevent

Description

Carbon dioxide Reduction Catalyst using Graphitic Frustrated Lewis Pair and Carbon dioxide Reduction Battery System in Seawater using the same

The present invention relates to a carbon dioxide reduction battery system in seawater using a graffiti incomplete Lewis acid-base pair catalyst. It relates to a battery system that can prevent

Due to the increase in CO ₂ emission and the increase in dissolved CO ₂ concentration in seawater due to the existing fossil fuel-based power generation system, global warming and acidification of seawater continue to deepen, threatening the global ecosystem.

Research on electrocatalysts that convert CO ₂ into industrial raw materials in addition to reduction of CO 2 has been continuing since 1869, but due to the chemically stable structure of CO ₂ , which avoids electrons and holes, high energy for chemical conversion is needed

To overcome this, with the advancement of sophisticated quantum calculation methods and electrocatalyst structure implementation and synthesis, it was found that the key reaction of CO ₂ conversion is carboxylation, and metals with good performance (Cu, Pt, Au, Ag, Mo, Pd , Co, Pb, Sn, Ce), MOF (Metal-Oranic-Framework), and carbon nanomaterial-based electrocatalysts have been studied.

Such an electrocatalyst provides an activation site for converting CO ₂ by electron-deficient metal-center or electron-rich diatomic species and electrochemically converts CO ₂ into methane, It can be converted into industrial raw materials such as methanol, formic acid and acetic acid.

However, since most expensive rare metals are used, and CO ₂ reduction reaction is possible only under high external voltage in an electrolyte environment in which CO ₂ based on organic solvents, strong acids (pH 1), or strong bases (pH 14) is supersaturated, , is fundamentally unsuitable for performing CO ₂ conversion in atmospheric CO ₂ concentrations (0.016 mM) and seawater (pH ˜8.2).

Korean Patent No. 10-1833755

The carbon dioxide reduction battery system in seawater according to the present invention is to solve the above problems, and an object of the present invention is to introduce a heterogeneous element or a Lewis acid and a base as a pair on a graphene framework using an ultrasonic spray synthesis method for a reduction reaction An object of the present invention is to provide a battery system capable of efficiently reducing carbon dioxide using a catalyst having an increased active site.

On the one hand, the present invention

a cathode composed of carbon nanomaterials in which Lewis acid and base components are paired with each other and introduced into the molecule;

an anode made of metal; and

seawater electrolyte; including,

Carbon dioxide dissolved in the seawater reacts with Lewis acid and base components of the carbon nanomaterial of the negative electrode,

Graffiti incomplete Lewis acid-base pair (GFLP) catalyst, characterized in that the oxygen of the carbon dioxide is reduced through an exothermic reaction while securing multiple active sites by forming a dynamic covalent bond with each of the carbon to the Lewis acid and the carbon to the Lewis base, respectively It provides a carbon dioxide reduction battery system in seawater using

On the other hand, the present invention

In the catalyst for carbon dioxide reduction,

graphene; and

Consists of; Lewis acid and base components arranged in pairs in the graphene molecule;

A graphic incomplete Lewis acid-base pair (GFLP), characterized in that the oxygen of carbon dioxide forms a covalent bond with the Lewis acid, and the carbon dioxide forms a covalent bond with the Lewis base, so that the carbon dioxide is reduced A catalyst for reducing carbon dioxide is provided.

The battery system according to the present invention not only uses a catalyst that overcomes the limitations of durability and catalyst reforming of conventional catalysts without using expensive rare metals as an anode, but also has excellent economic feasibility and reduces dissolved carbon dioxide in seawater by 80% With the above efficiency, it can be converted into multi-carbon compounds such as ethanol and propanol.

In addition, as the carbon dioxide in seawater is reduced using the battery system, the pH increases, thereby preventing seawater acidification.

1 shows the ultrasonic spray synthesis method and properties of the BN-GFLP structure according to an embodiment of the present invention ((A) Schematic diagram of the USC process for BN-GFLP synthesis and molecular interaction between BN-GFLP and CO ₂ (B) Survey XPS scans (normalized to C1s) and (C) EPR spectra of GN, N-GN, B-GN and BN-GFLP at 10 K. (D) ³¹ P MAS NMR spectra of TMP at BN-GFLP (E) ¹ H MAS NMR spectrum of pyrrole adsorbed to BN-GFLP).
2 is a graph showing the control of nitrogen doping concentration (A) and boron doping concentration (B) in graphene nanopowder according to an embodiment of the present invention.
3 is a graph showing the electrochemical reduction of carbon dioxide in the BN-GFLP electrode in seawater according to an embodiment of the present invention.
Figure 4 is a graph showing the CO ₂ R performance of the negative electrode physically mixed with B-GN and N-GN in the carbon dioxide reduction battery system in seawater according to an embodiment of the present invention.
Figure 5 confirms the electrical energy storage and stability during CO ₂ R in the carbon dioxide reduction battery system in seawater according to an embodiment of the present invention ((A) a schematic diagram of a jig-type CBS system. (B) 36 driven by the CBS system (C) Change in seawater pH in CO ₂ R with a fixed current density of 0.13 mA cm ⁻² (pH is controlled via carbon dioxide bubbling in seawater) (D) BN-GFLP and control GN Galvanostatic charge-discharge voltage plot of a jig-shaped CBS cell with cathode).
Figure 6 shows the DFT calculation of the BN-GFLP catalyst for CO ₂ R according to an embodiment of the present invention.
7 is a graph showing HPLC and ESI-MS results of a BN-GFLP catalyst according to an embodiment of the present invention.
8 is a graph showing the quantitative CO ₂ reduction efficiency and the selectivity (selectivity, 95%) for the multi-carbon (C ₂₊ ) product for the reduction product of the BN-GFLP catalyst according to an embodiment of the present invention.

Hereinafter, the present invention will be described in more detail.

Carbon dioxide reduction battery system in seawater using a graffiti incomplete Lewis acid-base pair (GFLP) catalyst according to an embodiment of the present invention,

a cathode composed of carbon nanomaterials in which Lewis acid and base components are paired with each other and introduced into the molecule;

an anode made of metal; and

seawater electrolyte; including,

Carbon dioxide dissolved in the seawater reacts with Lewis acid and base components of the carbon nanomaterial of the negative electrode,

It is characterized in that the oxygen of the carbon dioxide is reduced through an exothermic reaction while securing multiple active sites by forming dynamic covalent bonds with the Lewis acid and the carbon with the Lewis base, respectively.

The carbon dioxide reduction battery (CO ₂ Reduction Battery in Seawater, CBS) system according to the present invention uses a graffiti incomplete Lewis acid-base pair (GFLP) catalyst prepared using ultrasonic spray synthesis (USC) as a negative electrode. It is characterized in that (see FIG. 1).

The GFLP catalyst has a structure in which a heterogeneous element is doped on graphene, and more specifically, a Lewis acid and a base component are arranged in pairs in a graphene molecule.

FLP (Frustrated Lewis Pair) refers to a structural compound of a Lewis acid-base pair having a dynamic equilibrium state due to steric properties, and an electron acceptor of an acid (Acid, A) and an electron of a base (Base, B) They all have electron donor properties.

Therefore, the Lewis acid _and base pair is an incompletely bonded Lewis pair ( Frustrated Lewis Pairs (FLPs) are formed, whereby their respective activities can be maintained.

Conventionally, in the case of using a general transition metal, there was one active site, but since the active site becomes two due to the respective activities of the Lewis acid and the base, it is heated at room temperature by the peer mechanism. Dynamic covalent bonding between the CO ₂ molecule and C ... B and O ... A is formed, thereby converting the carbon dioxide into multiple carbons such as ethanol and propanol can be reduced to a substance.

After oxygen and carbon of carbon dioxide form covalent bonds with Lewis acids and bases, respectively, methanol is basically CO ₂ + 6H ⁺ + 6e ^- , ethanol is CO ₂ + 12H ⁺ + 12e ^- , propanol is CO ₂ + 18H ⁺ + 18e ^- The electrochemical reaction produces a reduction product, and in the case of multi-carbon products (ethanol, propanol), the reaction can proceed after the spontaneous generation of the C ₂ O ₃ intermediate in which the first intermediate CO and the second CO ₂ are combined. have.

In addition, as the carbon dioxide in the seawater is reduced, the pH of the acidified seawater may exhibit an effect of increasing from about 6.4 to 8.0.

In one embodiment of the present invention, the FLP (Frustrated Lewis Pair) is bonded to a carbon nanomaterial, that is, a graphic framework, and π-electrons from the graphic framework are continuously applied to the active site of the FLP. As it can be supplied with

In one embodiment of the present invention, the catalyst uses an ultrasonic spray synthesis method, which is a unique dual atom introduction method, so that there are few restrictions on acidic and basic dopant selection, and quantum mechanically high activation by cavitation by high frequency in an ultrasonic nozzle Using energy (5000 °C, 2000 atm), reaction and atomic bonding are possible within a few microseconds, and diatoms can be uniformly introduced throughout the graphene molecule.

In one embodiment of the present invention, the Lewis acid component may be one selected from the group consisting of boron, tin, zinc, copper, bismuth, molybdenum, tungsten and vanadium, and the Lewis base component is nitrogen, oxygen, sulfur, phosphorus , selenium, tellurium, arsenic, and may be one selected from the group consisting of antimony, but is not limited thereto.

The Lewis acid component is specifically bis (pinacolato) diboron (Bis (pinacolato) diboron), it is preferable to use a metal chloride (Metal chloride), etc., the Lewis base component is specifically as a gaseous phase, N ₂ , It is preferable to use O ₂ , but is not limited thereto.

In one embodiment of the present invention, the carbon nanomaterial may use graphene, reduced graphene oxide (rGO), carbon nanotubes, carbon nanofibers, graphite, or activated carbon, but is not limited thereto. .

In one embodiment of the present invention, the metal used for the positive electrode may include sodium, lithium, nickel, manganese, or alloys and oxides of the above metals, but is not limited thereto.

A catalyst for carbon dioxide reduction using a graphic incomplete Lewis acid-base pair (GFLP) according to an embodiment of the present invention,

In the catalyst for carbon dioxide reduction,

graphene; and

Consists of; Lewis acid and base components arranged in pairs in the graphene molecule;

Oxygen of carbon dioxide forms a covalent bond with the Lewis acid, and carbon of carbon dioxide forms a covalent bond with the Lewis base, whereby the carbon dioxide is reduced.

In one embodiment of the present invention, the catalyst for carbon dioxide reduction using a graffiti incomplete Lewis acid-base pair (BN-GFLP) doped with heteroelement of boron and nitrogen is a CO ₂ reduction catalyst and a cathode of a carbon dioxide reduction battery at the same time. ) can play a role. During the discharging process of the carbon dioxide reduction battery, the BN-GFLP anode reduces CO ₂ , and the reduction product is analyzed by high performance liquid chromatography (HPLC) and electrospray ionization mass spectroscopy (ESI-MS) to obtain a CO ₂ reduction product (methanol , ethanol and propanol) can be identified (see FIG. 7).

In addition, through the internal standard method of HPLC, quantitative CO ₂ reduction efficiency for each product (Faradaic efficiency, 87.6%) and selectivity for multi-carbon (C ₂₊ ) products (Selectivity, 95%) can be calculated. And (see FIG. 8), the mechanism of how to reduce CO ₂ to a multi-carbon product by the catalyst structure of BN-GFLP through Gibbs energy calculation can be elucidated theoretically.

Since the graffiti incomplete Lewis acid-base pair (GFLP) according to the present invention can exhibit superior performance than conventional metal and non-metal catalysts, it can be used as a variety of electrochemical devices such as fuel cells, supercapacitors, and dye-sensitized solar cells as well as batteries. applicable.

Hereinafter, the present invention will be described in more detail by way of Examples. These examples are only for illustrating the present invention, and it will be apparent to those skilled in the art that the scope of the present invention is not limited to these examples.

Example 1: Preparation of Heteroatom Doped GFLP by Ultrasonic Spray Synthesis (USC)

Example 1-1: Preparation of precursor solution

A solution in which graphene nanopowder and boron dopant bis(pinacolato)diboron) (bis(pinacolato)diboron) were dissolved in N-methyl-2-pyrrolidone using an ultrasonic nozzle using a syringe pump It was possible to create a vacuum bubble inside the solution by passing through it and applying high-frequency ultrasound (180 kHz). The GN precursors in these bubbles can form ions or radicals, which can react directly with the boron dopant and inert nitrogen gas.

More specifically, graphene nanopowder (15 mg) was added to NMP (30 mL) and sonicated with an ultrasonic probe (750 W, 20 kHz, Sonics and Materials Inc., USA) for 2 hours. to form a spray solution of 0.5 mg mL ^-1 . The spray solution was directly used to synthesize N-GN using N ₂ gas as a Lewis base dopant through USC. To synthesize B-GN and BN-GFLP, Lewis acid dopant or Bis(pinacolato)diboron) (30 mg) as a boron dopant (30 mg) was used in the GN spray prepared above. A precursor solution was prepared by adding to the solution (0.5 mg mL ^-1 , 30 mL) and sonicating for 1 hour.

Examples 1-2: Ultrasonic Spray Synthesis

Simultaneously pumped spray coatings were performed with an ExactaCoat system fixed with an impact ultrasonic nozzle (Sono-Tek Co.). The prepared precursor solution was sequentially supplied to an ultrasonic nozzle (180 kHz) system at a spray rate of 0.3 mL min ^-1 . Adjust the nozzle-to-substrate distance to 10 cm, and use compressed N ₂ or Ar gas pressure (3.0 psi) under the conditions of a temperature of 150 °C, a spray rate of 20 mm s ^-1 5 cm x 5 cm, thickness: ~ 4.1 mm). Then, the prepared product was cooled to room temperature and washed with water, ethanol and acetone to remove unreacted precursors and impurities. The residual solvent was evaporated in a vacuum oven at 200 °C for 24 h.

As a result, GN (including Ar gas carrier) and N-GN (including N ₂ gas carrier) catalyst cathodes were prepared through the USC process using GN spray solution as a precursor solution. In addition, B-GN (including Ar gas carrier) and BN-GFLP (including N ₂ gas carrier) catalyst cathodes were prepared through the USC process using a GN solution mixed with boron dopant.

1B, X-ray photoelectron spectroscopy (XPS) showed that the prepared carbon nanomaterial was 3.1 at% B in B-GN, 4.1 at% N in N-GN, and 6.8 at% B and 4.2 in BN-GFLP. It was confirmed that a high heteroatom doping concentration of at% N was achieved.

Referring to Figure 1C, the heteroatom doped GNs exhibited paramagnetic properties of less than 10 K due to the presence of radical defects from the doped B and N as measured by electron paramagnetic resonance (EPR) spectroscopy. This radical defect of BN-GFLP contributes to accelerating the first adsorption step of CO ₂ to its surface.

1D and 1E, Lewis Acid (LA) and Lewis Base (LB) of BN-GFLP are characterized by magic angle radiation nuclear magnetic resonance (MAS NMR). First, the acidity was measured by ³¹ P MAS NMR using the phosphorus probe molecule ³¹ P-trimethylphosphine (TMP) adsorbed to the BN-GFLP sample (see Fig. 1D). A δ ³¹ P peak at 35.47 ppm was observed on BN-GFLP, which could be assigned to the physical adsorption of TMP oxide (TMPO) on the surface of BN-GFLP by reaction of TMP with oxygen functional groups. The δ ³¹ P peak at 55.04 ppm appeared when TMPO was chemisorbed on the LA boron site of BN-GFLP, which corresponds to a Lewis acidity ranging from 50 to 55 ppm. The Brønsted acid peak of BN-GFLP appeared at -8.79 and -15.69 ppm by the adsorbed TMP, but the signal was weak.

Next, pyrrole was used as a probe for ¹ H MAS NMR to determine basicity (see Figure 1E). The strong peak at 5.95 ppm is assigned to the proton of the aromatic pyrrole ring. Compared with the normal peak of the NH group at pyrrole (8.26 ppm), the pyrrole adsorbed on the BN-GFLP sample was ¹ H at the shoulder peak at about 13.89 ppm due to hydrogen bonding interaction with the LB nitrogen in BN-GFLP. A large chemical shift was observed. This result is similar to the chemical shift observed in KX zeolite, which is known as a superbasic material. It is also noteworthy that in the ³¹ P and ¹ H MAS NMR results, the broadened peaks of the LA and LB sites are caused by the π-electron donating ability of the sp ² -hybridized framework of BN-GFLP.

Referring to FIG. 2 , the heteroatom doping content of GN was controlled by the N ₂ pressure (see FIG. 2A ) and the concentration of boron dopant (see FIG. 2B ). Referring to Figure 2A, the N doping content of GN in X-ray photoelectron spectroscopy (XPS) analysis, according to the pressure of the impact N ₂ carrier gas in USC, from 0.76 at% (0.5 psi) to 4.10 at% (3.0 psi) in the USC. could be precisely controlled. In addition, referring to FIG. 2B, in order to control the boron doping content of GN, by optimizing the concentration of the boron dopant solution in the USC process from 0.5 to 3.0 mg/ml, the doped boron content was changed from 1.08 at % to 3.20 at %. increased linearly. At boron dopant concentrations higher than 3.0 mg/ml, undesirable borate functionality increased in B-GN due to unreacted boron dopant (bis(pinacolato) diboron). It was confirmed that the higher boron content (6.8 at%) in BN-GFLP could be induced by BN bond formation in the presence of B and N dopants of the USC process.

Example 2: CO ₂ CO in Reduced Seawater Battery System (CBS) ₂ R selectivity evaluation

A Swagelok-type CBS system consisting of a modified 2465-type coin cell with Na-ion superionic conductor membrane (NaSICON) capable of forming an aprotic electrolyte-based seawater hybrid system was fabricated. The CBS can be connected to a pressure measuring system to continuously measure the change in internal CO ₂ gas pressure during the discharge process.

Then, the selectivity of the carbon dioxide reduction reaction (CO ₂ R) of BN-GFLP to the hydrogen evolution reaction (HER) was quantitatively verified through in situ analysis using an electrochemical mass spectrometry (DEMS) system (see Fig. 3). . The pressure decay of the Swagelok-type CBS cell filled with pure CO ₂ gas was monitored during the electrochemical discharge process. 3A and 3C show the constant current discharge voltage profile of the prepared catalyst electrode at a fixed current density of 0.13 mA cm ^-2 and the corresponding CO ₂ reduction results, respectively. The observed stable voltage stabilization with the linear drop of the consumed CO ₂ gas shows that the co-doped BN-GFLP provides a lower CO ₂ reduction overpotential and significantly improved CO ₂ reduction performance than the GN, N-GN and B-GN catalysts. gave.

The single-heteroatom-doped catalyst B-GN showed a _high CO2 reduction but similar overpotential to the control (GN), whereas the N-GN single catalyst electrode showed _a low overpotential but CO2 consumption similar to the control. appeared to be From these results, it was found that LA enhances the catalytic activity, whereas LB can increase the reaction rate.

Therefore, BN-GFLP of the FLP structure can increase the CO ₂ R efficiency through the synergistic effect of LA and LB. In particular, physically mixed N-GN and B-GN showed CO ₂ R performance completely different from BN-GFLP (see FIG. 4 ).

In addition, linear sweep voltammetry (LSV) analysis of the two-electrode Swagelok-type CBS system was performed under different gas atmospheres to further confirm the CO ₂ R selectivity for HER (see FIGS. 3B and D). As shown in Figure 3B, the LSV curve of BN-GFLP is CO ₂ R (2.6V vs Na/Na ⁺ ) in the seawater electrolyte saturated with CO ₂ and HER (1.7V vs Na/Na ⁺ ) in the Ar saturated state. ) showed a large difference in the starting potential between In particular, as a result of internal pressure collapse and real-time DEMS measurement of the Swagelok-type CBS system, it was found that CO ₂ decreased to 2.0 V and H ₂ gas generation occurred at a sweep voltage of 1.8 V (see FIG. 3D ). These results are consistent with the starting potentials of the constant current discharge (Fig. 3A) and the LSV curve (Fig. 3B). Therefore, it was confirmed that BN-GFLP showed reliable CO ₂ R selectivity compared to HER.

3E and F, ¹¹ B and ¹⁵ N NMR spectroscopic analysis was performed to confirm the capacity of BN-GFLP to bind CO ₂ . Prior to CO ₂ gas stimulation, BN-GFLP exhibited a broad ¹¹ B peak due to heterogeneous boron doping in the graphite framework ( FIG. 2E ). In contrast, a remarkably strong ¹¹ B signal at 27.58 ppm associated with BO binding was observed in BN _- GFLP with CO2. For ¹⁵ N NMR, the isotope ¹⁵ N urea was used as the ¹⁵ N dopant in BN-GFLP.

In the absence of CO ₂ , the ¹⁵ N NMR spectrum showed a broad peak at 64.41 ppm from ¹⁵ N in the graphite backbone of the BN-GFLP sample ( FIG. 3F ). On the other hand, two sharp peaks at 71.05 and 91.72 ppm appeared due to two NC interaction modes in BN-GFLP containing CO ₂ . The bidentate coordination of NC and BO corresponds to a more downshifted peak at 91.72 ppm due to the charge localization effect compared to the monodentate NC coordination at 71.05 ppm. Through these NMR results, it was confirmed that CO ₂ was adsorbed to BN-GFLP through boron, so that LA binds to oxygen of CO ₂ and LB binds to carbon.

Referring to Figure 5, for actual CO ₂ R operation in a seawater environment, a jig (Zig) type CBS cell was prepared. Under CO ₂ bubbling, the jig-shaped CBS cell provided sufficient electrical energy to operate the light emitting diode (LED) device ( FIG. 5B ). In addition, in order to reflect the natural ocean acidification caused by anthropogenic CO ₂ emission, CO ₂ saturated seawater was prepared with CO ₂ bubbling for 2 hours, and the pH was drastically reduced to 6.4. The acidic seawater electrolyte was restored by the CO ₂ R activity of the BN-GFLP cathode, and the pH gradually increased from 6.4 to 8.0 after 90 hours of CBS discharge ( FIG. 5C ). The charge-discharge cycle stability of the CBS cell under CO ₂ atmosphere was well maintained for 200 h with a lower discharge-charge overpotential than that of the GN catalyst (Fig. 5D).

As a result of analyzing the reduced CO ₂ produced during the discharging process of the CBS cell by high performance liquid chromatography (HPLC) and electrospray ionization mass spectroscopy (ESI-MS), methanol, ethanol and propanol were detected (FIG. 7), the HPLC Through _the internal standard _of It was proven to be superior (FIG. 8).

The precipitation of CaCO ₃ during the CO ₂ R process in seawater can be caused by a local increase in pH, which is known to be a major stability problem of metallic CO ₂ R catalysts. In the CBS system according to the present invention, even after intentionally adding 0.5M CaCl ₂ to the seawater electrolyte, CaCO ₃ was not detected on the BN-GFLP surface, and only the C ₂₊ product was detected. These results show that BN-GFLP according to the present invention has high reactivity to HCO ₃ ⁻ and CO ₂ reduction before formation of CaCO ₃ .

Referring to FIG. 6 , density functional theory (DFT) calculations were performed to confirm the C ₂₊ production mechanism of the BN-GFLP catalyst for CO ₂ R (see FIG. 6A ).

BN-GFLP was confirmed to bind more strongly to CO ₂ in the bidentate structures of NC and BO than in the monodentate structures of NC according to ¹¹ B and ¹⁵ N MAS NMR analysis. In addition, the bidentate structure can form carbon monoxide (CO) intermediates starting from CO ₂ and HCO ₃ ⁻ with a favorable Gibbs energy (ΔG) of -1.4 eV. Direct CC bond coupling between the CO intermediate and another CO ₂ results in the formation of C ₂ O ₃ with a very stable ΔG of approximately -3.2 eV.

In addition, the energy levels of all species on BN-GFLP exhibit Gibbs free binding energies favorable for the conversion of CO ₂ to C ₂₊ such as ethanol and propanol. The crystalline phase of the overall reaction is the first CO formation (*CO ₂ H + H ⁺ + e ^- → *CO + H ₂ O), calculated to be 1.57 eV uphill at U = 0 V. Through this, it was found that the DFT-calculated free energy of CO ₂ R on BN-GFLP can form C ₂₊ from CO ₂ in seawater.

In summary, a CO ₂ reduction battery (CBS) system for reducing dissolved CO ₂ in seawater was developed using a heteroelement doped graphic incomplete Lewis acid-base pair (GFLP) catalyst cathode according to the present invention, and 87.6% Faraday efficiency to recover acidic seawater. In addition, the GFLP according to the present invention can provide a new double CO ₂ bonding mode to provide a useful multi-carbon product in CO ₂ R by exothermic CC coupling, and is environmentally friendly and can be used as an electrochemical catalyst in various fields do.

As the specific part of the present invention has been described in detail above, for those of ordinary skill in the art to which the present invention pertains, it is clear that these specific techniques are only preferred embodiments, and the scope of the present invention is not limited thereto. do. Those of ordinary skill in the art to which the present invention pertains will be able to make various applications and modifications within the scope of the present invention based on the above contents.

Accordingly, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (8)

a cathode composed of carbon nanomaterials in which Lewis acid and base components are paired with each other and introduced into the molecule;
an anode made of metal; and
seawater electrolyte; including,
Carbon dioxide dissolved in the seawater reacts with Lewis acid and base components of the carbon nanomaterial of the negative electrode,
Graffitially incomplete Lewis acid-base pair (GFLP) catalyst, characterized in that the oxygen of the carbon dioxide is reduced through an exothermic reaction while securing multiple active sites by forming dynamic covalent bonds with the Lewis acid and the carbon with the Lewis base, respectively Carbon dioxide reduction battery system in seawater using According to claim 1, wherein the Lewis acid component is characterized in that one selected from the group consisting of boron, tin, zinc, copper, bismuth, molybdenum, tungsten and vanadium, a graffiti incomplete Lewis acid-base pair (GFLP) catalyst Carbon dioxide reduction battery system in seawater using According to claim 1, wherein the Lewis base component is nitrogen, oxygen, sulfur, phosphorus, selenium, tellurium, arsenic and antimony, characterized in that one selected from the group consisting of, Graffitially incomplete Lewis acid-base pair (GFLP) ) Catalyst-based carbon dioxide reduction battery system in seawater. According to claim 1, wherein the carbon nanomaterial is graphene, reduced graphene oxide (reduced grapheme oxide, rGO), carbon nanotubes, carbon nanofibers, graphite or activated carbon, characterized in that the graphitic incomplete Lewis acid- Carbon dioxide reduction battery system in seawater using base pairing (GFLP) catalysts. According to claim 1, wherein the metal is sodium, lithium, nickel, manganese, characterized in that one selected from the group consisting of alloys and oxides of the metals, Seawater using a graffiti incomplete Lewis acid-base pair (GFLP) catalyst My carbon dioxide reduction battery system. The battery system for reducing carbon dioxide in seawater using a graffiti incomplete Lewis acid-base pair (GFLP) catalyst according to claim 1, wherein the pH of seawater increases as the carbon dioxide is reduced to prevent acidification of seawater. The carbon dioxide reduction battery system in seawater using a graffiti incomplete Lewis acid-base pair (GFLP) catalyst according to claim 1, wherein the carbon dioxide is reduced and converted into ethanol and propanol. In the catalyst for carbon dioxide reduction,
graphene; and
Consists of; Lewis acid and base components arranged in pairs in the graphene molecule;
A graphic incomplete Lewis acid-base pair (GFLP), characterized in that the oxygen of carbon dioxide forms a covalent bond with the Lewis acid and the carbon of carbon dioxide forms a covalent bond with the Lewis base, so that the carbon dioxide is reduced A catalyst for the reduction of carbon dioxide.

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