Hydrogen isotope exchange catalyst complex and method for producing the same

Abstract

This invention provides a hydrogen isotope exchange catalyst composite and a method for producing the same, which are highly practical in terms of their applicability. This composite possesses hydrophobic properties, preventing the phenomenon of liquid water covering the catalyst while simultaneously not hindering water molecules from approaching the catalyst, and ensuring very good efficiency in the hydrogen isotope exchange reaction. Furthermore, it ensures excellent reaction efficiency without depending on the hydrophobicity of the matrix. [Solution] A catalyst complex for hydrogen isotope exchange is provided, comprising a catalyst support containing a metal-organic structure composite having an open metal site (OMS) and pores; a hydrophobic modifying compound introduced into the OMS; and a metal catalyst for hydrogen isotope exchange introduced into the pores.

Description

[Technical Field]

[0001] The present invention relates to a hydrogen isotope exchange catalyst composite and a method for producing the same, and more specifically, to a hydrogen isotope exchange catalyst composite and a method for producing the same that is hydrophobic, prevents the phenomenon of liquid water covering the catalyst, while simultaneously not hindering water molecules from approaching the catalyst, and can ensure very good efficiency of the hydrogen isotope exchange reaction, and can ensure excellent reaction efficiency without depending on the hydrophobicity of the support, and is extremely excellent in terms of its applicability. [Background technology]

[0002] To date, the majority of electrical energy is still produced from coal, gas, and oil, which inevitably has the potential to lead to a climate crisis, and as a result, nuclear power generation has become increasingly active recently. However, if tritium-contaminated water and other materials generated during such nuclear power generation processes are discharged into the environment, they can cause serious health problems. Furthermore, tritium (T) and deuterium (D) are extremely important resources, used either as raw materials for nuclear fusion or as core raw materials for next-generation technologies such as semiconductors and organic light-emitting diodes, so there is a need to separate and recover them not only for environmental reasons but also for other reasons.

[0003] However, light hydrogen (H), deuterium (D), and tritium (T) have similar chemical properties, making separation difficult. Therefore, a recently reported separation method uses an isotope exchange reaction between water and hydrogen gas to separate the isotopes. This method has attracted considerable attention because it offers a fairly high isotope separation rate and hydrogen gas does not exhibit any particular toxicity.

[0004] The isotope exchange reaction between water and hydrogen gas primarily involves a metal catalyst, but because it is a reaction between a liquid and a gas, its efficiency is problematic. This is because the liquid condenses in bulk form on the metal catalyst, blocking contact between the catalyst and the gas, and inhibiting the reaction between the liquid and the gas.

[0005] Conventionally, to solve such problems, methods have been used that focus on macroscopic water repellency and directly disperse a metal catalyst in a hydrophobic polymer-based matrix, or disperse it in a non-hydrophobic support and then disperse it using a hydrophobic polymer-based matrix or binder. However, such conventional methods only impart hydrophobic properties to the catalyst matrix and only achieve macroscopic hydrophobicity. As a result, there is still a problem that the reaction efficiency is not excellent because water still covers the catalyst or the inflow of water molecules to the catalyst in the microscopic environment is completely blocked.

[0006] In addition, such conventional methods depend on the hydrophobicity of the polymer constituting the matrix, so the selection of the matrix is limited. As a result, there is also a problem that it is impossible to form the catalyst complex in a free form, which is disadvantageous from the perspective of its usability.

[0007] Therefore, it is required to develop a catalyst complex for hydrogen isotope exchange that is very excellent from the perspective of usability, which can maintain hydrophobicity, prevent the phenomenon of water molecules covering the catalyst, and at the same time ensure very good efficiency of the hydrogen isotope exchange reaction, and can ensure excellent reaction efficiency without depending on the hydrophobicity of the matrix.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0009] The present invention was proposed to solve the problems described above, and aims to provide a hydrogen isotope exchange catalyst composite that is hydrophobic, prevents the phenomenon of liquid water covering the catalyst, does not hinder water molecules from approaching the catalyst, ensures very good efficiency of the hydrogen isotope exchange reaction, and ensures excellent reaction efficiency without depending on the hydrophobicity of the matrix, and is therefore extremely excellent in terms of its applicability. [Means for solving the problem]

[0010] In order to solve the aforementioned problems, the present invention provides The present invention provides a hydrogen isotope exchange catalyst complex comprising: a catalyst support containing a metal-organic structure composite having an open metal site (OMS) and pores; a hydrophobic modifying compound introduced into the OMS; and a hydrogen isotope exchange metal catalyst introduced into the pores.

[0011] Furthermore, the hydrogen isotope exchange catalyst complex may further include a catalyst matrix, in which the catalyst support may be dispersed within the catalyst matrix.

[0012] Furthermore, the water contact angle of the metal-organic structure composite may be 90° or more.

[0013] Furthermore, the water contact angle of the metal-organic structure composite is 90° or more, and the water vapor diffusivity is 5x10 -14 cm 2 It can be / s or more.

[0014] Furthermore, the hydrophobic modified compound may be a compound represented by chemical formula 1. <Chemical formula 1> [ka]

[0015] In this case, the functional group (Fn) is -NH2, -NH-, -NRH, -N=, -NR2, -C5H5N, -OH, -COOH, -PH2, -PO3 2- It is one of the following: -SH R1 is one of the following: a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C1-C20 aryl group, and a C1-C20 heteroaryl group.

[0016] Furthermore, the hydrophobic modifying compound may contain one or more selected from the group consisting of dodecylamine, decylamine, octylamine, hexylamine, aniline, and benzylamine.

[0017] Furthermore, the metal catalyst for hydrogen isotope exchange may contain one or more elements selected from the group consisting of Pt, Pd, Ir, Rh, Re, Ni, Co, W, Cu, Au, Ag, Mo, and Fe.

[0018] Furthermore, the catalyst matrix may be a hydrophobic polymer matrix.

[0019] Furthermore, the hydrogen isotope exchange catalyst complex may further contain a binder, and the catalyst support may be bound together by the binder.

[0020] Furthermore, in order to solve the aforementioned problems, the present invention provides a method for producing a hydrogen isotope exchange catalyst complex, comprising the steps of (1) preparing a metal-organic structure (MOF) having an OMS (Open Metal Site) and pores; (2) introducing a hydrophobic modifying compound into the OMS of the metal-organic structure to form a hydrophobic modified metal-organic structure complex; and (3) reacting the hydrophobic modified metal-organic structure complex with a catalyst matrix to disperse it inside the catalyst matrix, wherein the step of introducing a hydrogen isotope exchange metal catalyst into the pores is performed between steps (1) and (2) or between steps (2) and (3).

[0021] Furthermore, the water contact angle of the hydrophobic-modified metal-organic structure composite may be 90° or greater.

[0022] Furthermore, the hydrophobic modified compound may be a compound represented by chemical formula 1. <Chemical formula 1> [ka]

[0023] In this case, the functional group (Fn) is -NH2, -NH-, -NRH, -N=, -NR2, -C5H5N, -OH, -COOH, -PH2, -PO3 2- It is one of the following: -SH R1 is one of the following: a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C1-C20 aryl group, and a C1-C20 heteroaryl group.

[0024] Furthermore, in order to solve the aforementioned problems, the present invention provides a hydrogen isotope exchange catalyst complex produced by the method described above. [Effects of the Invention]

[0025] Through the present invention, it is possible to provide a hydrogen isotope exchange catalyst composite that is hydrophobic, prevents the phenomenon of liquid water covering the catalyst, while simultaneously not hindering water molecules from approaching the catalyst, and ensures very good efficiency in the hydrogen isotope exchange reaction. At the same time, it is possible to ensure excellent reaction efficiency without depending on the hydrophobicity of the matrix, and from the viewpoint of its usability, it is possible to provide a hydrogen isotope exchange catalyst composite that is extremely excellent. [Brief explanation of the drawing]

[0026] [Figure 1] Figure 1 is a schematic diagram showing the manufacturing process of a hydrogen isotope exchange catalyst complex according to a preferred embodiment of the present invention. [Figure 2] Figure 2 is a schematic diagram illustrating a hydrogen isotope exchange reactor. [Figure 3]Figure 3 shows the results of XRD (X-ray diffraction) analysis performed on Example 1, Comparative Example 1, Comparative Example 2, and Example 2 of the present invention. [Figure 4] Figure 4 shows the adsorption curves obtained after N2 adsorption experiments were conducted on Comparative Example 1 and Comparative Example 2 of the present invention. [Figure 5] Figure 5 shows the results of measuring the stomatal size distribution using nonlocal density functional theory, based on Figure 4, which is the N2 adsorption curve for Comparative Examples 1 and 2 of the present invention. [Figure 6] Figure 6 shows the results of FT-IR analysis performed on Example 1 and Comparative Examples 1 and 2 of the present invention. [Figure 7] Figure 7 shows the morphology of the nanocrystals for Example 1, Comparative Example 1, Comparative Example 3, and Example 2 of the present invention, as captured using a scanning electron microscope (SEM). [Figure 8] Figure 8 shows the results of high-angle annular dark-field imaging analysis performed using HAADF-STEM on Example 2 of the present invention. [Figure 9] Figure 9 shows the results of mapping Pt to Example 2 of the present invention using EDS analysis. [Figure 10] Figure 10 shows the results of mapping Cr, C, O, and N to Example 2 of the present invention using EDS analysis. [Figure 11] Figure 11 is a photograph of Example 2 of the present invention taken with a TEM (transmission electron microscope). [Figure 12] Figure 12 is a 10-fold magnification of Example 2 of the present invention compared to Figure 11, and was captured using a TEM (transmission electron microscope). [Figure 13] Figure 13 shows the results of XPS (X-ray electron spectroscopy) analysis performed to analyze the oxidation state of platinum contained in Comparative Example 3, Comparative Example 3, and Example 2, in which the platinum reduction step is not performed, in the present invention. [Figure 14]Figure 14 shows the results of XANES (X-ray absorption near edge structure) analysis performed on Example 2 of the present invention, compared with the results for Pt foil, PtO2, and H2PtCl6 (a precursor of the platinum catalyst). [Figure 15] Figure 15 shows the results of EXAFS (Extended X-ray absorption fine structure) analysis performed on Example 2 of the present invention, compared with the results for Pt foil and PtO2. [Figure 16] Figure 16 shows the water vapor adsorption isotherms obtained for Comparative Example 1, Comparative Example 3, and Example 2 in order to measure water repellency after the introduction of the hydrophobic modifying compound in the present invention. [Figure 17] Figure 17 shows the results of evaluating the degree of water vapor diffusion for Comparative Example 1 and Comparative Example 2 in order to measure the change in the degree to which water molecules come into contact with the catalyst due to the introduction of a hydrophobic modifying compound in the present invention. [Figure 18] Figure 18 shows the experimental results for Comparative Examples 1 and 2 of the present invention, at 25°C and 90% relative humidity. The x-axis is set to s1 / 2 and the y-axis to the ratio of water vapor adsorption amount over time to the maximum water vapor adsorption amount for the water vapor adsorption isotherm. The figure then shows the results fitted to each of these results using Fick's diffusion coefficient model. [Figure 19] Figure 19 shows photographs of the water contact angles evaluated for Example 1, Comparative Example 1, Comparative Example 2, and Example 2 of the present invention. [Figure 20] Figure 20 shows the results after impregnating Pt@MIL-101 / PVDF, which was prepared by dispersing Example 1 and Comparative Example 3 of the present invention in PVDF using the same method as in Example 1, with deionized water for 5 seconds and evaluating its macroscopic water repellency. [Figure 21] Figure 21 shows the results of measuring the column efficiency over time for Example 1 of the present invention. [Figure 22a]Figure 22a shows a comparison of the column efficiency with respect to temperature for Pt@MIL-101 / PVDF produced by dispersing Example 1 and Comparative Example 3 of the present invention in PVDF using the same method as in Example 1. [Figure 22b] Figure 22b shows a comparison of column efficiency by G / L value for Pt@MIL-101 / PVDF produced by dispersing Example 1 and Comparative Example 3 of the present invention in PVDF using the same method as in Example 1. [Figure 22c] Figure 22c shows the column efficiency measured after reacting Example 1 of the present invention for 28 days, and the percentage of the column efficiency value on day 1. [Figure 23a] Figure 23a shows the results of in situ DRIFTs (In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy) analysis performed on MIL-101-12 / PVDF produced by dispersing Example 1, Comparative Example 1, and Comparative Example 2 in PVDF using the same method as in Example 1, and Pt@MIL-101 / PVDF produced by dispersing Comparative Example 3 in PVDF using the same method as in Example 1. [Figure 23b] Figure 23b is a magnified view of the region where a bond was formed with H2O in the in situ DRIFTs spectrum for Example 1 of the present invention. [Figure 23c] Figure 23c is a magnified view of the region where a bond was formed with D2O in the in situ DRIFTs spectrum for Example 1 of the present invention. [Figure 23d] Figure 23d shows the in situ drift spectra results for Comparative Example 1 of the present invention and Pt@MIL-101 / PVDF. [Figure 24] Figure 24 is a schematic diagram showing the behavior of H2O molecules and D2O molecules in Example 1 of the present invention. [Figure 25] Figure 25 shows the in situ drift spectral results of the MIL-101-12 / PVDF of the present invention. [Figure 26]Figure 26 shows an SEM image taken after irradiating Example 1 of the present invention with radiation. [Figure 27] Figure 27 shows the results of FT-IR analysis performed on Example 1 and Comparative Example 2 of the present invention after irradiation with radiation. [Figure 28] Figure 28 shows the results of XRD analysis performed on Example 1 and Comparative Example 2 of the present invention after irradiation with radiation. [Figure 29] Figure 29 shows the results of XPS analysis performed on Example 1 and Comparative Example 2 of the present invention after irradiation with radiation. [Modes for carrying out the invention]

[0027] The embodiments of the present invention will be described in detail below so that they can be easily implemented by a person with ordinary skill in the art to which the present invention pertains. The present invention can be embodied in a variety of different forms and is not limited to the embodiments described herein.

[0028] As mentioned above, conventional hydrogen isotope exchange catalyst complexes rely solely on the hydrophobicity of the catalyst matrix. Despite introducing hydrophobicity through the matrix, liquid water still covers the catalyst surface, or the inflow of water molecules into the catalyst is completely blocked, resulting in poor reaction efficiency. Furthermore, their reliance on the matrix's hydrophobicity limits matrix selection, which is a significant disadvantage from a practical standpoint.

[0029] Accordingly, the present invention provides a catalyst complex for hydrogen isotope exchange, comprising a catalyst support containing a metal-organic structure composite having an open metal site (OMS) and pores; a hydrophobic modifying compound introduced into the OMS; and a metal catalyst for hydrogen isotope exchange introduced into the pores, thereby seeking to solve the aforementioned problems.

[0030] Through this process, compared to conventional hydrogen isotope exchange catalyst complexes, a catalyst complex is provided that prevents liquid water from covering the catalyst while allowing the hydrogen isotope exchange reaction to proceed smoothly, resulting in excellent reaction efficiency and independence from the hydrophobicity of the matrix. This makes it extremely advantageous in terms of its applicability.

[0031] First, the hydrogen isotope exchange catalyst complex according to the present invention includes a catalyst support comprising a metal-organic structure complex having an open metal site (OMS) and pores.

[0032] More specifically, the metal-organic structure complex includes a metal-organic framework (MOF). In this context, the metal-organic framework refers to a porous material in which metal clusters and organic linkers (organic bridging ligands) are linked by coordination bonds to form a three-dimensional structure. A variety of metal-organic frameworks can be formed by selecting metal ions and organic ligands. Such metal-organic frameworks have pores inside, and the size of these pores can be adjusted by changing the type of organic linker or metal cluster. Compared to other porous materials, they are highly versatile and have excellent ability to support catalysts internally. Furthermore, these metal-organic frameworks have a very large specific surface area, and when a catalyst is introduced inside, they can achieve very high reaction efficiency compared to other porous materials. They also possess a robust structure and exhibit excellent chemical and thermal stability.

[0033] The inclusion of such metal-organic structures in hydrogen isotope exchange catalyst complexes results in significantly superior reaction efficiency compared to the introduction of other porous materials. Furthermore, their excellent chemical stability allows for stable operation even in radioactive environments exposed to tritium. Additionally, by appropriately adjusting the pore size, catalyst loss can be prevented, enabling stable hydrogen isotope exchange reactions over extended periods.

[0034] More specifically, the metal-organic structure can be used without limitation as long as it is applicable to the hydrogen isotope exchange catalyst complex. For example, the metal cluster may contain one or more metals selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, Ce, and La. Preferably, it may contain one or more metals selected from the group consisting of chromium, vanadium, iron, nickel, cobalt, copper, zinc, titanium, and manganese. Furthermore, not only the metal itself but also any compound of a metal can be used without limitation as the metal source.

[0035] Furthermore, in the case of the metal-organic structure organic linker, any organic substance having a coordinating functional group is possible. Examples of coordinating functional groups include carboxylic acid groups, carboxylic acid anionic groups, amino groups (-NH2), imino groups (=NH2), amide groups (-CONH2), sulfonic acid groups (-SO3H), sulfonic acid anionic groups (-SO3-), methanedithio acid groups (-CS2H), methanedithio acid anionic groups (-CS2-), pyridine groups, or pyrazine groups. To derive a more stable metal-organic structure material, organic substances with two or more coordinating sites, such as bidentates or tridentates, are advantageous. As for organic substances, if there are coordinating sites, neutral organic substances such as bipyridine and pyrazine, anionic organic substances such as carboxylate anions (exemplified by terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, glutarate, succinate, etc.) are possible, as well as cationic substances. In the case of carboxylic acid anions, any anion is possible, including those with aromatic rings such as terephthalate, linear carboxylic acid anions such as formate, and anions with non-aromatic rings such as cyclohexyl dicarbonate. Organic compounds that have coordinating sites are possible, as are those that have potentially coordinating sites and change to become coordinating under reaction conditions. That is, even if an organic acid such as terephthalic acid is used, it can bond with the metal component via terephthalate after the reaction. Typical examples of organic compounds that can be used include organic acids selected from benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, naphthalentricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid, formic acid, oxalic acid, malonic acid, succicic acid, glutaric acid, hexanediic acid, heptanediic acid, or cyclohexyldicarboxylic acid, as well as their anions, pyrazines, bipyridines, etc. It is also possible to use a mixture of one or more organic compounds.

[0036] Such metal-organic structures may be one or more selected from the group consisting of MIL-101, HKUST-1, MOF-74, MOF-808, PCN-222, MIL-125, MIL-53, and MOF-5, and preferably one or more selected from the group consisting of MIL-101, HKUST-1, and MOF-74. In this case, when the metal-organic structure is one or more selected from the group consisting of MIL-101, HKUST-1, and MOF-74, it is highly advantageous in that the metal-organic structure can be synthesized in large quantities, the compound can be easily introduced into the OMS, and it has excellent usability.

[0037] More specifically, the metal-organic structure contained in the hydrogen isotope exchange catalyst complex according to the present invention has pores. A hydrogen isotope exchange metal catalyst, described later, may be supported in these pores. In this case, the average size of the pores is not particularly limited, but is preferably 0.5 to 20 nm. If the pore size is less than 0.5 nm, diffusion of the substance is not easy, contact between the catalyst and the reactants becomes difficult, which is disadvantageous from the viewpoint of reaction efficiency. Also, if the average size of the pores exceeds 20 nm, the specific surface area decreases as the pores become very large, which is disadvantageous from the viewpoint of reaction efficiency, and the catalyst may easily desorb.

[0038] Furthermore, the pore size can be appropriately adjusted depending on the type of catalyst and the reaction environment. In this case, to adjust the pore size, the type of metal-organic structure can be appropriately selected, or more specifically, the composition of the metal clusters and organic linkers that make up the metal-organic structure can be appropriately selected.

[0039] More specifically, a metal catalyst for hydrogen isotope exchange may be introduced into the aforementioned pores. The metal catalyst for hydrogen isotope exchange acts as a catalyst for the hydrogen isotope exchange reaction between water and hydrogen gas. In this case, reaction equation 1 below shows the reaction equation for the isotope exchange reaction between water and hydrogen gas. Here, I is one or more elements selected from the group consisting of deuterium (D) or tritium (T).

[0040] <Reaction Equation 1> [ka]

[0041] More specifically, the type of catalyst is not limited as long as it can act as a catalyst for the hydrogen isotope exchange reaction between water and hydrogen gas, but more specifically, it may include one or more selected from the group consisting of Pt, Pd, Ir, Rh, Re, Ni, Co, W, Cu, Au, Ag, Mo, Fe and the group consisting of oxides or sulfides thereof, or it may include an alloy containing one or more selected from the group consisting of Pt, Pd, Ir, Rh, Re, Ni, Co, W, Cu, Au, Ag, Mo, Fe. In this case, preferably, the metal catalyst for hydrogen isotope exchange may be one or more selected from the group consisting of Pt, Pd, Ni, Au. When the metal catalyst is one or more selected from the group consisting of Pt, Pd, Ni, Au, it is advantageous in that the catalytic efficiency for the hydrogen isotope exchange reaction is very good.

[0042] More specifically, the hydrogen isotope exchange metal catalyst may have an average diameter of 0.5 to 5 nm. In this case, if the average diameter of the hydrogen isotope exchange metal catalyst is less than 0.5 nm, the stability of the catalyst decreases, side reactions such as aggregation occur, which is unfavorable from the standpoint of maintaining catalytic performance. If the average diameter exceeds 5 nm, the specific surface area of ​​the catalyst decreases, and the proportion of atoms that actually come into contact with the reactants decreases, which is unfavorable from the standpoint of reaction efficiency.

[0043] More specifically, the hydrogen isotope exchange metal catalyst may be added to the metal-organic structure in an amount of 0.5 to 30% by weight. In this case, if the hydrogen isotope exchange metal catalyst is included in an amount of less than 0.5% by weight, the hydrogen isotope reaction may not proceed smoothly due to the small amount of catalyst, and in order to ensure an absolute amount of isotope exchange metal catalyst inside the hydrogen isotope exchange catalyst complex, a large amount of metal-organic structure complex must be used, which is disadvantageous from an economic standpoint. Furthermore, if the hydrogen isotope exchange metal catalyst is included in an amount exceeding 30% by weight, problems may occur such as clogging of the pore structure of the metal-organic structure or a decrease in specific surface area, leading to a decrease in catalytic performance.

[0044] More specifically, the metal-organic structure contained in the hydrogen isotope exchange catalyst complex according to the present invention has an OMS (open metal site). An OMS refers to a site in a metal cluster, in particular a position adjacent to the metal within a metal cluster formed by removing a ligand or other chemical oligomer. Various types of compounds may be attached to the metal cluster or the metal inside the metal cluster via the OMS, thereby allowing control of the physical properties of the metal-organic structure.

[0045] In the case of the aforementioned metal-organic structure, it is possible to use one in which the OMS has already been formed, or to use one in which the OMS has been artificially formed. In this case, the method for forming the OMS is not limited to any method that can form the OMS on a metal-organic structure, but for example, it can be formed by heat treatment to remove water or solvent components contained in the metal-organic structure.

[0046] In this case, any compound having a functional group that can bind to the OMS can be attached without restriction, allowing for control of the physical properties of the metal-organic structure. When using a metal-organic structure with an OMS, controlling its physical properties is easy, which is very advantageous from the standpoint of its usability. Furthermore, any compound having a functional group that can bind to the OMS can be introduced into the OMS by a simple method, such as mixing the compound to be attached with the metal-organic structure and heating it, making the introduction of the compound simple. Metal-organic structures with an OMS allow for the introduction of compounds and control of their physical properties through such a simple process, which is far superior to the case of silica or other porous compounds such as porous carbon compounds, where controlling the physical properties is done through a very complex process and the range of control is limited.

[0047] More specifically, a hydrophobic modifying compound may be introduced into the OMS. In this case, the hydrophobic modifying compound is a compound having a hydrophobic portion, and by introducing this compound into the OMS, the physical properties of the metal-organic structure can be controlled to be hydrophobic.

[0048] Conventionally, as part of a means to increase the reaction efficiency in hydrogen isotope exchange reactions, a method of simply dispersing the hydrogen isotope exchange metal catalyst in a hydrophobic polymer has been used. However, this only ensures hydrophobicity or water repellency at a macroscopic level, and at a microscopic level, liquid water still condenses around the catalyst, still blocking gas contact, which is unfavorable from the viewpoint of reaction efficiency, or the approach of water molecules is completely blocked, which is also unfavorable from the viewpoint of reaction efficiency.

[0049] Thus, the present invention solves the aforementioned problems by introducing a hydrophobic modifying compound into the OMS and controlling the physical properties of the metal-organic structure itself to be hydrophobic. More specifically, the metal-organic structure has a metal catalyst for hydrogen isotope exchange supported in its internal pores and can catalyze the isotope exchange reaction between water and hydrogen gas. Thus, the hydrogen isotope exchange reaction between water and hydrogen gas that occurs as shown in reaction equation 1 above occurs more specifically by the following reaction equations 2 and 3. In this case, I is one or more selected from the group consisting of deuterium (D) or tritium (T).

[0050] <Reaction Equation 2> [ka]

[0051] <Reaction Equation 3> [ka]

[0052] <Reaction Equation 4> [ka]

[0053] <Reaction Equation 5> [ka]

[0054] <Reaction Equation 6> [ka]

[0055] <Reaction Equation 7> [ka]

[0056] <Reaction Equation 8> [ka]

[0057] Reaction equation 2 shows the vapor-liquid equilibrium equation between water and water vapor, and reaction equation 3 shows the hydrogen isotope exchange reaction equation between water vapor and hydrogen gas. Reaction equations 4 to 8 show the isotope exchange reaction between hydrogen and water molecules mediated by the catalyst, for example, when the catalyst is platinum. As mentioned above, the isotope exchange reaction between water and hydrogen gas essentially involves the reaction of water vapor and hydrogen gas. Therefore, for the hydrogen isotope exchange reaction to occur easily, the hydrophobicity of the catalyst must prevent the accumulation of H2O(l) on the catalyst surface, allowing for easy contact between the catalyst and hydrogen gas, while simultaneously enabling contact between water vapor and the catalyst, and facilitating easy contact between hydrogen gas and water vapor.

[0058] Consequently, if only macroscopic hydrophobicity is ensured, as in conventional methods, the two aforementioned properties cannot be achieved simultaneously, resulting in poor reaction efficiency. In contrast, in the hydrogen isotope exchange catalyst according to the present invention, a hydrophobic modifying compound is introduced into the metal-organic structure supporting the catalyst inside its pores, and its physical properties are controlled to be hydrophobic. This prevents bulk liquid water molecules from directly contacting the catalyst, while simultaneously allowing water vapor to come into very smooth contact with the catalyst through its internal pores, resulting in significantly improved hydrogen isotope exchange reaction efficiency compared to conventional methods.

[0059] According to a preferred embodiment of the present invention, the metal-organic structure composite may have a water contact angle of 90° or more. When the water contact angle of the metal-organic structure composite is 90° or more, it effectively blocks contact of liquid water with the catalyst, preventing the liquid from covering the catalyst surface and hindering contact between the catalyst and hydrogen gas. At the same time, water vapor can easily diffuse into the metal-organic structure and come into contact with the catalyst, resulting in significantly better efficiency of the hydrogen isotope exchange reaction compared to conventional methods. In this case, the water contact angle can be measured, for example, by dropping a water droplet onto the metal-organic structure composite and then measuring the contact angle at the point where the water droplet and the metal-organic structure composite come into contact.

[0060] At this time, more preferably, the metal-organic framework composite has a water contact angle of 90° or more and simultaneously an average water vapor diffusivity of 5×10 -14 cm 2 / s or more. When the water contact angle is 90° or more and the average water vapor diffusivity is 5×10 -14 cm 2 / s or more, the contact of the water in the liquid state with the catalyst is prevented as described above, and the effect that water vapor can easily diffuse into the metal-organic framework is maximized, and the efficiency of the hydrogen isotope exchange reaction is very remarkable compared with the prior art.

[0061] At this time, the average water vapor diffusivity is calculated based on the average water vapor diffusivity at a relative humidity of 0 to 100%. At this time, the water vapor diffusivity (D i ) at each relative humidity can be calculated after evaluating and plotting the time-dependent adsorption isotherm at each relative humidity and then fitting the adsorption isotherm with the Fick's diffusion coefficient model represented by the following calculation formula 1. The time-dependent adsorption isotherm shows the ratio of the amount of water vapor adsorbed over time to the maximum amount of water vapor adsorption with t 1 / 2 (s 1 / 2 ) on the x-axis at each relative humidity.

[0062] <Calculation formula 1>

Number

[0063] D i = Water vapor diffusivity M t = Total amount of solute at a specific time t M∞ = Total amount of solute at infinite time t = ∞ β = Mediating variable indicating the adsorption and desorption rate of the solute a = Pore radius

[0064] At this time, the average water vapor diffusivity is obtained by measuring the water vapor diffusivity for each of at least five arbitrarily selected relative humidity values and calculating the average thereof.

[0065] Let's explain this in more detail with reference to Figure 18. Figure 18 shows the x-axis relative to the water vapor adsorption isotherm at 25°C and 90% relative humidity. 1 / 2 This figure shows the experimental results plotted with the y-axis representing the ratio of water vapor adsorption amount over time to the maximum water vapor adsorption amount, and then fitted to each result using Fick's diffusion coefficient model from calculation formula 1. As can be seen from Figure 18, when the time-dependent water vapor adsorption isotherm is fitted, it matches well with Fick's diffusion coefficient model, so it can be said that it is reasonable to measure water vapor diffusivity using this model. Therefore, after performing the fitting as described above, D i By measuring the value, the degree of water vapor diffusion can be measured relative to the given relative humidity. This allows for the measurement of the average degree of water vapor diffusion by repeating the same process at various relative humidity levels.

[0066] More specifically, the hydrophobic modifying compound is a compound that can control the physical properties of a metal-organic structure to be hydrophobic, and may be a compound having a hydrophobic portion. The method for introducing the hydrophobic modifying compound into the OMS is not limited to any method of introducing the compound into the OMS of a metal-organic structure, but for example, the compound may be covalently or coordinately bonded to the OMS, and for this purpose, it can be introduced through a process of mixing the metal-organic structure having the OMS with the hydrophobic modifying compound and heating it.

[0067] More specifically, the hydrophobic modified compound may be a compound represented by the following chemical formula 1.

[0068] <Chemical formula 1> [ka]

[0069] In this case, the functional group (Fn) is -NH2, -NH-, -NRH, -N=, -NR2, -C5H5N, -OH, -COOH, -PH2, -PO3 2- It is one of the following: -SH R1 is one of the following: a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C1-C20 aryl group, and a C1-C20 heteroaryl group.

[0070] More specifically, the hydrophobic modified compound can be bonded to the OMS of the metal-organic structure via the functional group (Fn).

[0071] Furthermore, "alkyl group (R)" is generally understood to mean a linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. A Cn alkyl group means an alkyl group in which the heavy chain hydrocarbon chain of the alkyl group has n carbon atoms, and this may be substituted or unsubstituted.

[0072] Furthermore, "heteroalkyl group" refers to an alkyl group containing 1 to 4 heteroatoms selected from nitrogen (N), oxygen (O), and sulfur (S), where the nitrogen and sulfur atoms may be oxidized, and the nitrogen atom may be quaternized. The heteroalkyl group may be bonded to the rest of the molecule via carbon or heteroatoms. Also, Cn heteroalkyl group refers to a heteroalkyl group in which the hydrocarbon ring that is the heavy chain of the heteroalkyl group has n carbon atoms, which may be substituted or unsubstituted.

[0073] Furthermore, "aryl group" refers to a polyunsaturated, aromatic, hydrocarbon substituent that may be a single or multi-ring fused or covalently bonded together. Additionally, a Cn aryl group refers to an aryl group in which the hydrocarbon ring that forms the heavy chain of the aryl group has n carbon atoms, and this may be substituted or unsubstituted.

[0074] Furthermore, a "heteroaryl group" refers to an aryl group (or ring) containing 1 to 4 heteroatoms selected from nitrogen (N), oxygen (O), and sulfur (S) (in the case of a multiple ring, in each separate ring), where the nitrogen and sulfur atoms may be oxidized, and the nitrogen atom may be quaternized. The heteroaryl group may be bonded to the rest of the molecule via carbon or heteroatoms. Also, a Cn heteroaryl group refers to a heteroaryl group in which the hydrocarbon ring that is the heavy chain of the heteroaryl group has n carbon atoms, which may be substituted or unsubstituted.

[0075] Furthermore, in the expression "substituted or unsubstituted," "substituted" means that one or more hydrogen atoms in a hydrocarbon are each independently replaced by the same or different substituents. Useful substituents include, but are not limited to, the following:

[0076] Such substituents include: -F;-Cl;-Br;-CN;-NO2;-OH; C1-C20 alkyl groups substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; C1-C20 alkoxy groups substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; C1-C20 alkyl groups, C1-C20 alkoxy groups, C6-C30 aryl groups substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, or -OH; C1-C20 alkyl groups, C1-C20 alkoxy groups, -F, -Cl, -B It may be one or more selected from the group consisting of: C6-C30 heteroaryl groups substituted or unsubstituted with r, -CN, -NO2, or -OH; C5-C20 cycloalkyl groups substituted or unsubstituted with C1-C20 alkyl groups, C1-C20 alkoxy groups, -F, -Cl, -Br, -CN, -NO2, or -OH; C5-C30 heterocycloalkyl groups substituted or unsubstituted with C1-C20 alkyl groups, C1-C20 alkoxy groups, -F, -Cl, -Br, -CN, -NO2, or -OH; and groups represented by -N(G1)(G2). In this case, G1 and G2 may be independently of each other: hydrogen; C1-C10 alkyl groups; or C6-C30 aryl groups substituted or unsubstituted with C1-C10 alkyl groups, respectively.

[0077] More specifically, R1 can be hydrophobic. When R1 is hydrophobic, the introduction of a hydrophobic modifying compound into the OMS allows the properties of the metal-organic structure complex to be controlled to be hydrophobic. This introduces microscopic hydrophobicity into the hydrogen isotope exchange catalyst complex, preventing liquid water from covering the catalyst and negatively impacting catalytic efficiency, while not hindering the diffusion of water molecules and achieving excellent reaction efficiency.

[0078] In this case, according to a preferred embodiment of the present invention, the hydrophobic modifying compound may be one or more selected from the group consisting of dodecylamine, decylamine, octylamine, hexylamine, aniline, and benzylamine, and in this case, it is particularly excellent from the viewpoint of improving the efficiency of the hydrogen isotope exchange reaction.

[0079] More specifically, the hydrophobic modifying compound can bind to approximately 40-95% of the OMS of the metal-organic structure. In this case, if the hydrophobic modifying compound binds to more than 95% of the OMS, water molecules cannot easily approach the metal catalyst, which can reduce the efficiency of the hydrogen isotope exchange reaction. Also, if the hydrophobic modifying compound binds to less than 40% of the OMS, liquid water can cover the surface of the catalyst, which can reduce the efficiency of the hydrogen isotope exchange reaction.

[0080] According to one preferred embodiment of the present invention, the hydrogen isotope exchange catalyst complex according to the present invention further comprises a catalyst matrix, wherein the catalyst support is dispersed within the catalyst matrix.

[0081] More specifically, the catalyst matrix is ​​not limited as long as it can support and disperse the metal-organic structure complex as the catalyst matrix of the hydrogen isotope exchange catalyst complex. Furthermore, an appropriate composition can be selected without limitation so that it can be molded or composed to suit the form required at the application site. This is because, in the hydrogen isotope exchange catalyst of the present invention, hydrophobicity is introduced into the metal-organic structure complex itself, ensuring excellent reaction efficiency regardless of the composition or form of the catalyst matrix.

[0082] In this case, for example, the catalyst matrix may be one or more selected from the group consisting of polymer matrix, graphene, carbon nanotubes, and carbon nitride, preferably a hydrophobic polymer matrix, and more preferably one or more selected from the group consisting of polystyrene, polyvinylidene fluoride (PVDF), polyether ether ketone, polypropylene, polytetrafluoroethylene, polyethylene, polymethyl methacrylate, polychlorotrifluoroethylene, and polydimethylsiloxane. When the catalyst matrix is ​​a hydrophobic polymer matrix, it is superior in terms of the efficiency of the hydrogen isotope exchange reaction, and in particular, when the catalyst matrix is ​​one or more selected from the group consisting of polystyrene, polyvinylidene fluoride (PVDF), and polypropylene, it is very advantageous in that it is efficient in the hydrogen isotope exchange reaction and easy to process.

[0083] More specifically, the hydrogen isotope exchange catalyst complex may contain a metal-organic structure complex in an amount of 0.01 to 5% by weight relative to its total weight. In this case, if the metal-organic structure complex is contained in an amount of less than 0.01% by weight, the absolute amount of catalyst is insufficient, which is disadvantageous from the viewpoint of reaction efficiency of the hydrogen isotope exchange reaction. If the metal-organic structure complex is contained in an amount exceeding 5% by weight, the amount of metal-organic structure used is large, making it difficult to control the physical properties of the catalyst complex, which is disadvantageous from an economic standpoint.

[0084] More specifically, the catalyst matrix may be porous and have voids inside, and the metal-organic structure composite described later may be dispersed in these voids. More specifically, the average diameter of the voids in the catalyst matrix may be in the range of 0.002 μm to 10 μm. In this case, if the average diameter of the voids is less than 0.002 μm, mass transfer inside the catalyst matrix is ​​not smooth, which is unfavorable from the viewpoint of hydrogen isotope exchange reaction efficiency. If the average diameter of the voids exceeds 10 μm, problems may arise in that the metal-organic structure composite described later cannot be stably supported.

[0085] More specifically, the form of the metal-organic structure composite is not limited as long as it is a normal metal-organic structure form, but it may preferably be in the form of a powder, and more preferably in the form of a powder having an average diameter in the range of 1 nm to 0.1 mm. In this case, if the average diameter of the powder is less than 1 nm, it may be difficult to disperse within the catalyst matrix and prone to aggregation, which can cause problems in terms of handling. If the average diameter of the powder exceeds 0.1 mm, it is difficult to disperse uniformly within the catalyst matrix, and the specific surface area decreases, which is disadvantageous in terms of hydrogen isotope exchange reaction efficiency.

[0086] According to one preferred embodiment of the present invention, the hydrogen isotope exchange catalyst complex may further contain a binder, and the catalyst support may be bound together by the binder.

[0087] Conventional hydrogen isotope exchange catalysts rely solely on the matrix for their hydrophobicity, resulting in a significant decrease in catalytic efficiency when the hydrophobic matrix is ​​absent. Even when a hydrophobic matrix is ​​present, only macroscopic hydrophobicity is ensured, leaving the catalyst inefficient. The present invention addresses these issues by introducing hydrophobicity into the catalyst support itself, ensuring not only macroscopic but also microscopic hydrophobicity or water repellency. This results in superior efficiency in hydrogen isotope exchange reactions, even in the absence of a hydrophobic matrix.

[0088] Thus, the hydrogen isotope exchange catalyst complex according to the present invention may be in a form in which the catalyst support is bound together by a binder.

[0089] More specifically, the binder is not particularly limited as long as it is a compound capable of binding the catalyst support to such an extent that the hydrogen isotope exchange catalyst complex can be used as a catalyst in a particular hydrogen isotope exchange reaction, but is preferably one or more selected from the group consisting of ethylcellulose, polytetrafluoroethylene, polypropylene, and polystyrene.

[0090] More specifically, the hydrogen isotope exchange catalyst complex may contain a binder in an amount greater than 0% by weight and less than or equal to 20% by weight.

[0091] More specifically, the method for assembling the catalyst support via a binder is not limited to any method that can normally assemble the catalyst support using a binder, but could be, for example, a method of mixing the catalyst support and binder and then heat-pressing them together, or a method of mixing the catalyst support binder and solvent and then drying the solvent. In this case, the solvent can be any one or more selected from, for example, water and alcohol, as long as it can be used when assembling the catalyst support and binder.

[0092] More specifically, the hydrogen isotope exchange catalyst complex according to the present invention is not limited in its form as long as it is a form that a hydrogen isotope exchange catalyst complex can normally have, but it can have forms such as spherical or cylindrical, and its size is also not limited as long as it is a size that can normally be had, but it can be, for example, 1 to 10 mm with respect to its long axis.

[0093] Furthermore, the present invention provides a method for producing a hydrogen isotope exchange catalyst complex in order to solve the aforementioned problems. While this omits explanations of aspects that overlap with the aforementioned hydrogen isotope exchange catalysts, the invention is not limited to these.

[0094] The present invention provides a method for producing a hydrogen isotope exchange catalyst complex, comprising the steps of (1) preparing a metal-organic framework (MOF) having an open metal site (OMS) and pores; (2) introducing a hydrophobic modifying compound into the OMS of the metal-organic framework to form a hydrophobic modified metal-organic framework complex; and (3) reacting the hydrophobic modified metal-organic framework complex with a catalyst matrix to disperse it inside the catalyst matrix, wherein a step of introducing a metal catalyst for hydrogen isotope exchange into the pores is performed between steps (1) and (2) or between steps (2) and (3), thereby solving the aforementioned problems. The hydrogen isotope exchange catalyst complex produced by this method has microscopic hydrophobicity introduced, preventing liquid water from covering the catalyst and negatively impacting catalytic efficiency, while not hindering the diffusion of water molecules, and thus achieving excellent reaction efficiency in the hydrogen isotope exchange reaction.

[0095] First, in step (1), an OMS and a metal-organic structure having pores are prepared. In this step, a commercially available metal-organic structure can be used, or the metal-organic structure can be synthesized directly. The synthesis of the metal-organic structure can be carried out without restriction using any known method for the synthesis of metal-organic structures, for example, by hydrothermal methods. Furthermore, when carrying out step (1), the composition of the metal and organolinker contained in the metal-organic structure and the reaction conditions can be controlled to adjust the pore size of the metal-organic structure.

[0096] Furthermore, in the case of the metal-organic structure, it is possible to use one in which the OMS has already been formed, or to artificially form the OMS and use it. In this case, the method for forming the OMS is not limited to any method that can normally form an OMS on a metal-organic structure, but for example, it can be formed by heat treatment to remove water or solvent components contained in the metal-organic structure.

[0097] Next, in step (2), a hydrophobic modifying compound is introduced into the OMS of the metal-organic structure to form a hydrophobic modified metal-organic structure composite. The method for introducing the hydrophobic modifying compound into the metal-organic structure is not limited to any method that can normally introduce the compound into the OMS, but for example, it may be a method in which the metal-organic structure and the hydrophobic modifying compound are mixed and then heated to react. In this case, the reaction temperature and time can be appropriately selected depending on the type of metal-organic structure and the hydrophobic modifying compound, but for example, the reaction can be carried out at 0 to 150°C for 0.1 to 168 hours.

[0098] Furthermore, the metal-organic structure can be activated before introducing the hydrophobic modifying compound. There are no restrictions on the method of activation, but for example, it could be activated in a vacuum atmosphere at 40 to 350°C for 0.1 to 168 hours.

[0099] Furthermore, the step of introducing a hydrophobic modifying compound into the metal-organic structure can be performed either before or after the step of introducing a hydrogen isotope exchange catalyst into the metal-organic structure, as described later.

[0100] Next, in step (3), the hydrophobic modified metal-organic structure complex is reacted with the catalyst matrix and dispersed inside the catalyst matrix. More specifically, the dispersion method can be any commonly used method without limitation, but for example, if the catalyst matrix is ​​a polymer compound, the polymer compound and the metal-organic structure complex can be mixed and dispersed, and if the catalyst matrix is ​​an inorganic substance, the porous inorganic substance, the metal-organic structure complex and a binder can be mixed and then molded and dispersed. At this time, the metal-organic structure complex is dispersed inside the catalyst matrix and the catalyst matrix can be synthesized at the same time, and compounds normally required for synthesis may be added further.

[0101] Furthermore, the method for producing the hydrogen isotope exchange catalyst complex according to the present invention includes the step of introducing a hydrogen isotope exchange metal catalyst into the pores. The step of introducing the hydrogen isotope exchange metal catalyst may be performed between step (1) and step (2) or between step (2) and step (3).

[0102] More specifically, the method for introducing a hydrogen isotope exchange metal catalyst into a metal-organic structure can be any method that can normally introduce a metal catalyst into a metal-organic structure, but for example, it could be a method that uses a double solvent method to introduce the metal catalyst into the metal-organic structure.

[0103] More specifically, when introducing a hydrogen isotope exchange metal catalyst into a metal-organic structure, one can either introduce the hydrogen isotope exchange metal element by reacting it with the metal-organic structure, or by reacting a precursor of the hydrogen isotope exchange metal element with the metal-organic structure and then reducing it. In this case, the metal element precursor is not limited as long as it can be reduced to form a hydrogen isotope exchange catalyst in metallic form, but for example, it may be a compound containing an oxidized form of metal ion.

[0104] According to a preferred embodiment of the present invention, the hydrophobic modified metal-organic structure composite may have a water contact angle of 90° or more. When the water contact angle of the metal-organic structure composite is 90° or more, it effectively blocks contact of liquid water with the catalyst, preventing the liquid from covering the catalyst surface and hindering contact between the catalyst and hydrogen gas. At the same time, water vapor can easily diffuse into the metal-organic structure and come into contact with the catalyst, resulting in significantly better efficiency of the hydrogen isotope exchange reaction compared to conventional methods. In this case, the water contact angle can be measured, for example, by dropping a water droplet onto the metal-organic structure composite and then measuring the contact angle at the point where the water droplet and the metal-organic structure composite come into contact.

[0105] In this case, more preferably, the hydrophobic modified metal-organic structure composite has a water contact angle of 90° or more, and at the same time has an average water vapor diffusivity of 5 x 10⁻¹⁰ -14 cm 2 It can be greater than / s. The water contact angle is 90° or greater, and the average water vapor diffusivity is 5x10 -14 cm 2 When the value is greater than or equal to / s, the aforementioned effect of preventing contact between the liquid water and the catalyst and allowing water vapor to easily diffuse into the metal-organic structure is maximized, resulting in a significantly more efficient hydrogen isotope exchange reaction compared to conventional methods.

[0106] More specifically, the hydrophobic modified compound may be a compound represented by chemical formula 1.

[0107] <Chemical formula 1> [ka]

[0108] In this case, the functional group (Fn) is -NH2, -NH-, -NRH, -N=, -NR2, -C5H5N, -OH, -COOH, -PH2, -PO3 2- It is one of the following: -SH

[0109] R1 is one of the following: a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C1-C20 aryl group, and a C1-C20 heteroaryl group.

[0110] More specifically, R1 can be hydrophobic. When R1 is hydrophobic, the introduction of a hydrophobic modifying compound into the OMS allows the properties of the metal-organic structure complex to be controlled to be hydrophobic. This introduces microscopic hydrophobicity into the hydrogen isotope exchange catalyst complex, preventing liquid water from covering the catalyst and negatively impacting catalytic efficiency, while not hindering the diffusion of water molecules and achieving excellent reaction efficiency.

[0111] More specifically, the present invention provides a hydrogen isotope exchange catalyst complex produced by the method for producing the hydrogen isotope exchange catalyst complex described above.

[0112] By producing a hydrogen isotope exchange catalyst complex using the manufacturing method described above, the produced catalyst complex is given microscopic hydrophobicity, preventing liquid water from covering the catalyst and negatively impacting catalytic efficiency, while not hindering the diffusion of water molecules, thereby achieving excellent reaction efficiency.

[0113] Furthermore, the present invention provides a hydrogen isotope exchange method utilizing the aforementioned hydrogen isotope exchange catalyst complex.

[0114] More specifically, the hydrogen isotope exchange method according to the present invention can also be performed by filling the inside of a catalyst column with the hydrogen isotope exchange catalyst complex, then injecting water from the top of the column and hydrogen gas from the bottom of the column to generate an isotope exchange reaction between the water and hydrogen gas.

[0115] In this case, the catalyst tower is not limited as long as it can support a hydrogen isotope exchange catalyst complex and can be used as a catalyst tower for a hydrogen isotope exchange reaction, but it may be made of glass, for example, and its form and size can be appropriately selected depending on its application and reaction scale.

[0116] In this case, for efficient fluid movement and reaction, the diameter of the catalyst tower may be 10 times or more the diameter of the catalyst complex, and the length of the catalyst tower may be 50 times or more the length of the catalyst complex.

[0117] Furthermore, the catalyst tower may further include a liquid inlet for introducing liquid and a gas inlet for introducing gas, and may further include a heating device for heating the liquid before introducing it into the liquid inlet in order to regulate the internal temperature. In this case, any ordinary heating device can be used without limitation, such as a hot plate.

[0118] Furthermore, the liquid inlet and gas inlet of the catalyst tower may be further equipped with flow rate control units for adjusting the flow rates of the liquid and gas. In this case, any flow rate control unit that normally adjusts the flow rates of liquid and gas can be used without limitation.

[0119] Furthermore, the gas inlet may have two or more inlets so that two or more types of gases can be injected, and each inlet may be further equipped with a flow rate adjustment unit so that the flow rate of each gas can be adjusted.

[0120] More specifically, the catalyst tower may further include a liquid outlet for discharging liquid and a gas outlet for discharging gas. In this case, water flowing into the liquid inlet may be discharged through the liquid outlet or further injected into the catalyst tower via a liquid circulation section. Thus, the catalyst tower may further include a liquid circulation section.

[0121] More specifically, water can flow into the catalyst tower through a liquid inlet, and hydrogen gas can flow in through a gas inlet. The incoming water and hydrogen gas both come into contact with the hydrogen isotope exchange catalyst complex, where a hydrogen isotope exchange reaction occurs in the catalyst, and hydrogen isotopes are exchanged between water and hydrogen. After the reaction, the water can be introduced into the liquid circulation section for further reaction, or it can be discharged to the outside through a liquid outlet. After the reaction, the hydrogen gas can be discharged through a gas outlet.

[0122] More specifically, a carrier gas may be injected into the gas inlet along with the hydrogen gas. The carrier gas can be used without limitation, but preferably it may be an inert gas that does not affect the hydrogen isotope exchange reaction, and more preferably it may be argon gas. [Examples]

[0123] The present invention will be described more specifically based on the following examples, but these examples are not intended to limit the scope of the present invention and should be understood as being for the purpose of aiding the understanding of the present invention.

[0124] <Example 1> 8.0 g of chromium(III) nitrate nonahydrate was dissolved in 9.5 ml of deionized water (DI) in a 500 mL Teflon liner. After complete dissolution, 3.32 g of terephthalic acid and 0.72 ml of hydrofluoric acid were added, and the mixture was vigorously stirred. The mixture was then autoclaved at 220 °C for 8 hours. After the reaction product was slowly cooled to room temperature, the mixture was filtered and washed twice with deionized water and DMF at 70 °C, with vacuum filtration between each washing step to obtain MIL-101. MIL-101 was then vacuum dried at 150 °C, and the activated MIL-101 was dispersed in anhydrous n-hexane. Then, while vigorously stirring, a 2.5 wt% aqueous solution of chloroplatinic acid hexahydrate (H2PtCl6·6H2O), a precursor of the platinum catalyst, was added dropwise at a rate of 15 μL / min using a syringe pump. Subsequently, the product was filtered, washed with ethanol, and dried overnight under vacuum at 150°C. The resulting powder was then reduced at 190°C under hydrogen conditions for 5 hours at a ramp rate of 2°C / min, followed by argon purging to obtain platinum-impregnated MIL-101, Pt@MIL-101. Next, for dodecylamine bonding, 1.0 g of activated Pt@MIL-101 and 1.0 g of dodecylamine were dispersed in 250 mL of cyclohexane at 150°C under vacuum. The mixture was then heated at 85°C for 48 hours and vacuum-filtered. The resulting powder was washed with DMF and dried overnight under vacuum at 120°C to obtain dodecylamine-bonded Pt@MIL-101, Pt@MIL-101-12. Finally, for the production of the Pt@MIL-101-12 / PVDF complex, deionized water was first mixed with DMF, and then lithium chloride was completely dissolved. Subsequently, Pt@MIL-101-12 was added and uniformly dispersed, then PVDF powder was added and vigorously mixed. The mixture was then heated and mixed overnight in a sealed container. At this time, the mass composition of the chemicals was as follows: PVDF 11.7 wt%, Pt@MIL-101-12 11.7 wt%, deionized water 1.1 wt%, lithium chloride 2.5 wt%, and the remainder was DMF. The uniformly mixed solution was then poured into a water tank filled with water, which is a non-solvent for PVDF, to replace the DMF in the solution and solidify the PVDF in fibrous form.Subsequently, the solvent in the water tank was sequentially replaced with fresh deionized water and hexane, and the fibers were left in each solvent for one day. After the solvent exchange process, the fibers were air-dried at room temperature and then further dried at 100°C under vacuum. The obtained final catalyst-polymer composite Pt@MIL-101-12 / PVDF was then prepared by cutting the fibers to lengths and diameters of approximately 3 mm and 1-2 mm, respectively.

[0125] <Example 2> Although manufactured in the same manner as in Example 1, only the process up to the introduction of dodecylamine was performed to obtain Pt@MIL-101-12.

[0126] <Comparative Example 1> The same MIL-101(Cr) material used in Example 1 was prepared.

[0127] <Comparative Example 2> Although manufactured in the same manner as in Example 1, the process of introducing platinum was omitted, and dodecylamine was introduced instead, resulting in MIL-101-12 in which dodecylamine was introduced into the metal-organic frame.

[0128] <Comparative Example 3> Although manufactured in the same manner as in Example 1, only the process up to the point of introducing platinum was performed to obtain Pt@MIL-101.

[0129] <Experimental Example 1 - XRD Analysis> XRD (X-ray diffraction) analysis was performed on Example 1, Example 2, Comparative Example 1, and Comparative Example 2, and the results are shown in Figure 3. Measurements were taken using an X-ray diffractometer (SmartLab, Rigaku) ​​with Cu Kα radiation (λÅ) while increasing the angle by 0.01° increments.

[0130] As can be seen from Figure 3, the XRD spectra of each example to comparative example are almost identical. However, in Examples 1, 2, and Comparative Example 2, the spectral intensity at 2θ = 5.8° decreased slightly, which is due to the introduction of dodecylamine, an amorphous alkyl chain, into the OMS. In addition, the spectrum of Example 1 changed slightly in the interval where 2θ is 4.5° or less, but this is not due to a change in the structure of the metal-organic structure, but rather to the amorphous properties of the polymer. Therefore, it can be confirmed that the structure of the metal-organic structure is maintained even with the introduction of dodecylamine and dispersion in PVDF.

[0131] <Experimental Example 2 - Texture Analysis> N2 adsorption experiments were conducted at cryogenic temperatures (77K) for Comparative Examples 1 and 2, and the adsorption curves are shown in Figure 4. Furthermore, the pore size distribution was measured using nonlocal density functional theory (NLDFT) based on the adsorption curves, and the results are shown in Figure 5. The BET (Brunauer-Emmett-Teller) surface area and pore size distribution are shown in Table 1. A physicoadscopy analyzer (Micromeritics, ASAP 2020) was used for the analysis.

[0132] [Table 1]

[0133] As can be seen from Figures 4 and 5 and Table 1, it can be confirmed that Comparative Example 2 showed a decrease in BET surface area, pore volume, and average pore diameter compared to Comparative Example 1. This is a change that occurred when dodecylamine was introduced into the metal-organic frame, and through this, it can be confirmed that dodecylamine was introduced correctly. From this, it can be inferred that dodecylamine was also introduced correctly in Examples 1 and 2, which were introduced using the same process.

[0134] <Experimental Example 3 - FT-IR Analysis> FT-IR analysis was performed on Examples 1 and 2 and Comparative Examples 1 to 3, and the results are shown in Figure 6. (400 cm) -1 ~4000cm -1 Measurements were taken using an FT-IR spectrometer (Thermo Fisher Scientific Instrument, Nicolet iS50) within the specified wavenumber range.

[0135] In all examples and comparative examples, 1505 cm was measured according to MIL-101. -1 , 1400cm -1 , 1010cm -1 and 745cm -1 We were able to observe a peak at . In addition, in Example 1, 1170 cm was observed due to the PVDF matrix. -1 , 880cm -1 , 840cm -1 A peak was observed at 2960 cm². In addition, in Example 1, Example 2, and Comparative Example 2, a peak was observed at 2960 cm². -1 and 2850cm -1 Two peaks could be observed, which are attributed to the CH bond of dodecylamine, suggesting that dodecylamine was successfully introduced in Example 1, Example 2 and the Comparative Example.

[0136] <Experimental Example 4 - SEM Imaging> The morphology of the nanocrystals in Example 1, Example 2, Comparative Example 1, and Comparative Example 3 was captured using a scanning electron microscope (SEM), and the resulting images are shown in Figure 7. An SEM (FEI company, Magellan 400) was used.

[0137] As can be seen from Figure 7, the octahedral shape, such as that of MIL-101, was maintained even after introducing Pt into its pores, and also after introducing dodecylamine. Furthermore, as shown in the photograph of Example 1, it can be confirmed that the octahedral structure of PVDF is uniformly dispersed and integrated within the PVDF matrix.

[0138] <Experimental Example 5 - Scanning Transmission Electron Microscopy (HAADF-STEM) and Energy-Dispersive X-ray Spectroscopy (EDS) Analysis> High-angle annular dark-field imaging analysis was performed on Example 2 using HAADF-STEM, and the results are shown in Figure 8. Pt was mapped using EDS analysis, and the results are shown in Figure 9. Mapping was also performed on Cr, C, O, and N, and the results are shown in Figure 10. For HAADF-STEM and EDS analysis, a STEM (Talos F200X G2, Thermo Fisher) was used.

[0139] As can be seen from Figures 8 and 9, the Pt particles are very uniformly dispersed within the Pt@MIL-101-12 of Example 2. Furthermore, as can be seen from Figure 10, the chromium, carbon, oxygen, and nitrogen are very uniformly distributed, which suggests that the dodecylamine was introduced very uniformly into the metal-organic structure.

[0140] <Experimental Example 6 - TEM Analysis> Experimental Example 2 was photographed using a TEM (transmission electron microscope), and the resulting image is shown in Figure 11. Additionally, four TEM images were randomly selected, and the diameters of 50 dark spots were measured randomly for each image. Their distribution is also shown in Figure 11. Furthermore, after taking another TEM image at 10x magnification compared to Figure 11, the resulting image is shown in Figure 12. This observation was performed using a TEM (FEI, Tecnai Ge F30 S-Twin) under a 300kV electron beam.

[0141] As can be seen from Figure 11, the Pt particles are uniformly distributed, which is the same result as shown in Experimental Example 5. Furthermore, the calculations in Figure 12 showed that the average diameter of the Pt nanoparticles was 2.58 ± 0.52 nm, which is similar to the pore size of MIL-101 observed in Experimental Example 2, suggesting that the Pt nanoparticles were successfully introduced into the metal-organic structure. Similarly, in Figure 12, Pt particles with a diameter of 0.232 nm were also confirmed. In addition, the dark spots in Figure 12 appeared after the reduction of Pt, confirming that the dark spots are Pt particles.

[0142] <Experimental Example 7 - Inductively Coupled Plasma Atomic Emission Spectrometry Analysis> ICP-OES (Inductively Coupled Plasma Atomic Emission Spectrometry) analysis was performed on Examples 1, 2, and the Comparative Example to measure the Pt and Cr content, respectively. The results are shown in Table 2. Each example and comparative example was treated overnight in a vacuum oven at 120°C, and then measured using an ICP-OES instrument (Agilent, ICP-OES 720).

[0143] [Table 2]

[0144] As can be seen from Table 2, comparing Comparative Example 3 with Example 2, it can be seen that the total mass increased due to the attachment of alkyl chains by the introduction of dodecylamine, and the relative amounts of Pt and Cr decreased in part. Furthermore, in Example 1, which was produced by mixing Pt@MIL-101-12 and PVDF in a 1:1 mass ratio, it can be confirmed that the relative amounts of Cr and Pt were approximately half compared to Example 2. Through this, it can be confirmed that Pt was introduced into the metal-organic structure while maintaining almost the same initial amount, without being removed through the introduction of dodecylamine or dispersion within the PVDF.

[0145] <Experimental Example 8 - Elemental Analysis> Elemental analysis was performed on Example 2, and the results are shown in Table 3. A Flash 2000 series elemental analyzer (Thermo Scientific) was used for the analysis.

[0146] [Table 3]

[0147] As can be seen from Table 3, it can be confirmed that 2.54 wt% nitrogen was introduced into Example 2. This is because the nitrogen of dodecylamine was measured, and through this, it can be confirmed that dodecylamine was introduced into the metal-organic structure. Furthermore, based on the amount of chromium measured by ICP-OES analysis in Experimental Example 7 and the amount of nitrogen in Experimental Example 8, the N / Cr molar ratio of Example 2 was calculated to be 0.495. Comparing this to the theoretical N / Cr molar ratio of MIL-101, which is 0.667, it can be inferred that dodecylamine was introduced into 73.9% of the total OMS.

[0148] <Experimental Example 9 - XPS Analysis> XPS (X-ray electron spectroscopy) analysis was performed on Comparative Example 3 (which did not undergo the platinum reduction step) and Example 2 to analyze the oxidation state of the platinum contained in each, and the results are shown in Figure 13. For the analysis, an XPS instrument (Thermo Scientific, Nexsa G2) was used and Avantage data system software was used.

[0149] As can be seen in Figure 13, when comparing Comparative Example 3 without the platinum reduction step with Comparative Example 3 with platinum reduction, it was found that the peaks of 76.8eV and 73.6eV corresponding to Pt4f(+4) almost disappeared during reduction, while the peaks of 71.2eV and 74.4eV corresponding to Pt4f(0) were very dominant. Furthermore, this trend was maintained in Example 2 as well. This means that platinum is converted into a form that can function as a catalyst during the reduction process, and that this state is maintained even after the introduction of dodecylamine.

[0150] <Experimental Example 10 - XANES Analysis> To analyze the chemical state of the platinum catalyst introduced into the metal-organic structure, XANES (X-ray absorption near edge structure) analysis was performed on Example 2. The results were compared with those of Pt foil, PtO2, and H2PtCl6 (precursors of the platinum catalyst), and the results are shown in Figure 14. A wide XAFS instrument (Pohang light source, 10C) was used for the analysis.

[0151] As can be seen from Figure 14, the peak intensity in Example 2 is distinct from that of PtO2 and H2PtCl6, and can be confirmed to be almost identical to that of Pt foil. This indicates that the electronic state of platinum introduced into the metal-organic structure is almost identical to that of metallic Pt, meaning that platinum remains in a reduced state capable of functioning as a catalyst even after the production of the metal-organic structure composite.

[0152] <Experimental Example 11 - EXAFS Analysis> To analyze the chemical state of the platinum catalyst introduced into the metal-organic structure, EXAFS (Extended X-ray absorption fine structure) analysis was performed on Example 2, and the results were compared with those for Pt foil and PtO2, as shown in Figure 15. A Wide XAFS instrument (Pohang light source, 10C) was used for the analysis.

[0153] As can be seen from Figure 15, the main peak in Example 2 is very similar to that of Pt foil and different from that of PtO2, which indicates a dominant Pt-Pt coordination degree, and that the Pt-O coordination degree is at a negligible level. This means that the Pt nanoparticles introduced into the metal-organic structure complex exist mostly in a metallic state and are in a state where they can act as a catalyst for hydrogen isotope exchange reactions. Furthermore, the specific Pt-Pt coordination number is 9.46 ± 0.94, from which we can calculate that the average diameter of the nanoparticles is approximately 25 Å, which is consistent with the result that the average diameter of the nanoparticles in Experimental Example 6, described above, was 25.8 Å.

[0154] <Experimental Example 12 - Evaluation of Water Vapor Adsorption> To measure water repellency after the introduction of the hydrophobic modification compound, water vapor adsorption isotherms were obtained for Comparative Example 1, Comparative Example 3, and Example 2, and are shown in Figure 16. For evaluation, analysis was performed using a water vapor adsorption analyzer (TA instruments, VTI-SA+) at 25°C and relative humidity in the range of 4-90%, with measurements taken in 2% increments up to 60% relative humidity and in 10% increments thereafter. The measurement was performed by measuring the mass difference relative to a sample left undisturbed for 12 hours in a nitrogen atmosphere at 120°C. In this case, if the mass change over 5 minutes was less than 0.001 wt(%), it was considered to be in equilibrium, and the maximum equilibrium time for analysis was set to 6 hours.

[0155] As can be seen from Figure 16, in Comparative Examples 1 and 3, where the hydrophobic modifying compound was not introduced, the amount of water absorbed was very high. This is because after water molecules attached to the metal-organic structure OMS, a multimolecular water chain grew around the attached water molecules. In addition, in Comparative Example 3, it was confirmed that the maximum water adsorption capacity increased by 16.5% compared to Comparative Example 1 due to the introduction of hydrophilic Pt. In contrast, in Example 2, where the hydrophobic modifying compound was introduced, the water adsorption capacity decreased by 65.9% compared to Comparative Example 3, demonstrating excellent water repellency. Furthermore, in Comparative Examples 1 and 3, water absorption increased sharply in the 40% relative humidity range, but in Example 2, water absorption increased gradually at 45%, which is also due to the excellent microscopic hydrophobicity of the hydrophobic modifying compound. Thus, by introducing the hydrophobic modifying compound into the OMS, it is possible to prevent the bulk liquid water from covering the catalyst surface and blocking contact with hydrogen gas, compared to when the compound is not introduced into the OMS. As a result, the efficiency of the hydrogen isotope exchange reaction is significantly better than before.

[0156] <Experimental Example 13 - Evaluation of Water Vapor Diffusivity> To measure the change in the degree to which water molecules contact the catalyst due to the introduction of hydrophobic modifying compounds, the water vapor diffusivity was evaluated for Comparative Example 1 and Comparative Example 2, and the results are shown in Figure 17. For the analysis, a water vapor adsorption analyzer (TA instruments, VTI-SA+) was used at 25°C. In this case, the average water vapor diffusivity was calculated for relative humidity from 0 to 100%. In this case, the water vapor diffusivity (D) at each relative humidity was calculated. i The time-dependent adsorption isotherms were evaluated and plotted for each relative humidity, and then fitted to these adsorption isotherms using Fick's diffusion coefficient model, represented by the following formula 1, before calculation. The time-dependent adsorption isotherms were calculated for each relative humidity, t 1 / 2 (s 1 / 2 The x-axis is set to s, and this shows the ratio of water vapor adsorption amount over time to the maximum water vapor adsorption amount. Figure 18 shows the water vapor adsorption isotherm at 25°C and 90% relative humidity, with the x-axis set to s. 1 / 2This figure shows the experimental results, with the y-axis representing the ratio of water vapor adsorption amount over time to the maximum water vapor adsorption amount, and then shows the results fitted to each result using Fick's diffusion coefficient model from calculation formula 1.

[0157] <Formula 1>

number

[0158] D i = water vapor diffusion M t = Total amount of solute at a specific time t M ∞ =Total amount of solute over infinite time t=∞ β = parameter indicating the solute adsorption / desorption rate. a = radius of the stoma

[0159] As can be seen from Figure 17, water vapor diffusivity is almost unrelated to relative humidity, and the average water vapor diffusivity of Comparative Example 1 is 5.87 x 10⁻⁶. -13 The value is cm / s, and the comparative example 2 is 4.91 x 10 -13 The values ​​were cm / s, and there was no significant difference between the two. This means that, compared to Experimental Example 12, the introduction of the hydrophobic modifying compound prevents bulk liquid water from accumulating on the metal catalyst for hydrogen isotope exchange, while not hindering the approach of water molecules themselves. This is because microscopic hydrophobicity is introduced by the unique structure of the present invention, in which the metal catalyst for hydrogen isotope exchange is introduced inside the metal-organic structure into which the hydrophobic modifying compound has been introduced. As a result, the efficiency of the hydrogen isotope exchange reaction is maximized and is significantly superior to conventional methods.

[0160] <Experimental Example 14 - Evaluation of Water Contact Angle> To evaluate macroscopic water repellency, the water contact angle was evaluated for Example 1, Comparative Example 1, Comparative Example 2, and Example 2, and the resulting photographs are shown in Figure 19. For analysis, an angle analyzer (SEO, Phoenix 300) was used, and the analysis was performed using Surfaceware 9 software. For Comparative Example 1, Comparative Example 2, and Example 2, the powder was uniformly scattered on a glass plate for measurement, while for Example 1, a thin film was formed using the same configuration and manufacturing method, and then measured.

[0161] As can be seen from Figure 19, in Comparative Example 2 and Example 2, in which the hydrophobic modified compound was introduced, a water contact angle of 90° or more was observed, confirming that they possessed excellent macroscopic water repellency. This is a significant improvement compared to Comparative Example 1, which had almost no water repellency. Furthermore, in Example 1, in which a metal-organic structure composite was introduced into the PVDF, excellent macroscopic water repellency was also confirmed.

[0162] <Experimental Example 15 - Evaluation of Impregnation> Pt@MIL-101 / PVDF, prepared by dispersing Example 1 and Comparative Example 3 in PVDF using the same method as in Example 1, was impregnated with deionized water for 5 seconds, and its macroscopic water repellency was evaluated. The results are shown in Figure 20.

[0163] As can be seen from Figure 20, in Example 1, the original surface color was maintained even after immersion in deionized water for 5 seconds, indicating that bulk liquid water did not penetrate into the interior. In contrast, Pt@MIL-101 / PVDF showed a clear change in hue after immersion in deionized water for 5 seconds, indicating that water had penetrated. Furthermore, when immersed in deionized water, no bubbles were generated in Example 1, whereas bubbles were generated in Pt@MIL-101 / PVDF. This also means that water penetrated Pt@MIL-101 / PVDF, while it did not penetrate Example 1. Therefore, it was confirmed that the introduction of the hydrophobic modifying compound introduced microscopic hydrophobicity, effectively blocking direct contact between bulk liquid water and the metal catalyst for hydrogen isotope exchange.

[0164] <Experimental Example 16 - Evaluation of Column Efficiency> Column efficiency was evaluated to compare the actual efficiency of the hydrogen isotope exchange reaction in Pt@MIL-101 / PVDF, which was prepared by dispersing Example 1 and Comparative Example 3 in PVDF using the same method as in Example 1. Figure 2 is a schematic diagram of the isotope exchange reactor. More specifically, a catalytic reactor was prepared using a glass column with an inner diameter of 10 mm and a length of 150 mm. Water was allowed to flow at a constant rate from a liquid inlet located at the top of the reactor, and a hot plate and heating tape were placed in front of the liquid inlet to adjust the water temperature. In addition, hydrogen gas was allowed to be injected at a constant rate from a gas inlet located at the bottom of the reactor, and argon gas was introduced together as a carrier gas. After the reaction, the liquid escaped to the liquid outlet at the bottom. At this time, a porous glass filter was attached to the bottom to prevent the catalyst complex from flowing out of the liquid outlet and gas inlet located at the bottom. After the reaction, the gas escaped to the gas outlet at the top.

[0165] In this experiment, the amount of each hydrogen isotope exchange catalyst complex was adjusted so that the mass of platinum contained in each was 5 mg, and the flow rate of the injected water was fixed at 0.2 ml / min. The molar ratio of the gas-liquid flow rate was measured in the range of 0.5 to 20, and the temperature range was measured in the range of 40 to 80°C. In this experiment, deionized water was used as the liquid and hydrogen gas as the gas. Since deuterium differs from tritium only in its isotopic separation coefficient, the experimental results for deuterium can be applied to tritium with the same trend. After the reaction, the liquid product was collected and analyzed using an isotopic water analyzer (PICARRO, L2140-i) to measure its isotopic content. The concentration of deuterium atoms was measured at least eight times for a single deuterium atom, and the average of the last three measurements was applied. VSMOW2, SLAP2, GRESP, and IAEA 604 were used as standard solutions for the measurement. Furthermore, the measurement was taken 2 hours after the start of the reaction, because, as can be seen from Figure 21, the reaction enters a stable phase 90 minutes after the start of the reaction.

[0166] Furthermore, column efficiency was calculated using the following method.

[0167] <Formula 2>

number

[0168] η = Column efficiency y out = Atomic concentration of deuterium at the gas outlet y in = Atomic concentration of deuterium at the gas inlet y* out = Atomic concentration of deuterium at the gas outlet in theoretical equilibrium In this case, the column efficiency can be determined by the following method.

[0169] <Formula 3>

number

[0170] y out = Atomic concentration of deuterium at the liquid outlet y in = Atomic concentration of deuterium at the liquid inlet L = flow rate of the injected liquid G = flow velocity of the injected gas

[0171] <Formula 4>

number

[0172] Equation 3 shows the mass equilibrium equation, and the ratio of gas to liquid flow rates can be defined as shown in Equation 4. In this case, assuming that a situation is reached where a liquid and gas of a specific concentration injected into the column are in equilibrium upon discharge, using Equations 3 and 4 as a basis, the mass equilibrium equation for the equilibrium state can be derived as shown in Equation 5.

[0173] <Formula 5>

number

[0174] x* out = Atomic concentration of deuterium at the liquid outlet in theoretical equilibrium state

[0175] <Formula 6>

number

[0176] In this case, the partition coefficient between liquid and gas can be defined as shown in calculation formula 6, and x* out <<1, y* out Assuming <<1, the following formula 7 can be derived from formulas 5 and 6.

[0177] <Formula 7>

number

[0178] Unlike the process of deriving formula 7, x* out <<1, y* out If we do not assume <<1 and solve equations 5 and 6 simultaneously, x* out , y* out This can be calculated as shown in formulas 8 and 9 below.

[0179] <Formula 8>

number

[0180] <Formula 9>

number

[0181] In this case, y* derived through the above calculation formula 9 outBy substituting this into formula 5, the column efficiency can be derived, which allows for a quantitative comparison of the catalyst complex performance. Furthermore, the temperature-dependent separation coefficient (α) for the hydrogen isotope exchange reaction was calculated using formula 10 below.

[0182] <Formula 10>

number

[0183] As described above, the column efficiency was calculated, and the column efficiency was compared for Pt@MIL-101 / PVDF produced by dispersing Example 1 and Comparative Example 3 in PVDF using the same method as Example 1. The G / L value was fixed at 1.0, and the reaction was carried out while varying the temperature from 40°C to 80°C. The results are shown in Figure 22a. Furthermore, the column efficiency was compared when the temperature was fixed at 70°C, and the reaction was carried out while varying the G / L value from 0.5 to 2.0. The results are shown in Figure 22b. In addition, for Example 1, the column efficiency was measured after 28 days of reaction with the G / L fixed at 1.0 and the temperature fixed at 70°C, and the ratio to the column efficiency value on day 1 was measured and shown in Figure 22c.

[0184] As can be seen from Figures 22a and 22b, it can be confirmed that Example 1, in which the hydrophobic modifying compound was introduced, has significantly better column efficiency than Pt@MIL-101 / PVDF in which the hydrophobic modifying compound was not introduced. This suggests that microscopic hydrophobicity was directly introduced into the catalyst complex in Example 1, preventing bulk liquid water from covering the catalyst and preventing catalyst deactivation, while not hindering the approach of water vapor molecules, thus resulting in superior efficiency of the hydrogen isotope exchange reaction. Furthermore, as can be seen from Figure 22c, it can be confirmed that in the case of Example 1, the column efficiency remained at a nearly constant level for 28 days. This indicates that the catalyst complex according to the present invention maintains its ability to effectively block bulk liquid water in the hydrogen isotope exchange reaction while allowing appropriate water vapor access and preventing catalyst deactivation for a very long period of time.

[0185] Furthermore, the natural concentrations of deuterium in the deionized water and hydrogen gas used in this invention are 147 μmol / mol (D / (D+H)) and 135 μmol / mol (D / (D+H)), respectively, which are in the ultra-low isotope concentration range, close to the actual tritium concentration range of industrial wastewater. In Example 1, it was confirmed that the column efficiency was excellent even in this concentration range. Compared to conventional research on hydrogen isotope exchange catalysts, which has been conducted in the range of very high hydrogen isotope concentrations, this shows that the hydrogen isotope exchange catalyst complex according to the present invention can be applied much better to actual industrial environments than conventional methods.

[0186] <Experimental Example 17 - In situ DRIFTs Analysis> In situ DRIFTs (In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy) analysis was performed on MIL-101-12 / PVDF, prepared by dispersing Example 1, Comparative Example 1, and Comparative Example 2 in PVDF using the same method as Example 1, and on Pt@MIL-101 / PVDF, prepared by dispersing Comparative Example 3 in PVDF using the same method as Example 1. The overall spectrum result for Example 1 is shown in Figure 23a, the region where a bond with H2O was formed in the spectrum for Example 1 is shown in a magnified view in Figure 23b, the region where a bond with D2O was formed in the spectrum for Example 1 is shown in a magnified view in Figure 23c, and the spectral results for Comparative Example 1 and Pt@MIL-101 / PVDF are shown in Figure 23d. In addition, a schematic diagram of the behavior of H2O and D2O molecules in relation to Example 1 is shown in Figure 24. Furthermore, the spectral results for MIL-101-12 / PVDF are shown in Figure 25.

[0187] As can be seen from Figures 23b and 23c, in Example 1, the 3300 cm⁻¹ corresponds to the H₂O adsorption peak. -1 , 3360cm -1 The peak at 2423 cm² continuously decreases over time, corresponding to the D2O adsorption peak. -1 , 2507cm -1It can be confirmed that the corresponding peak continuously increases. This differs from Comparative Example 1 and Pt@MIL-101 / PVDF, which do not show such changes when compared with Figure 23d. This trend occurred in Example 1 because, before the introduction of D2O, the adsorbed H2O molecules were gradually replaced by D2O. The fact that this trend is not observed in Comparative Example 1 and Pt@MIL-101 / PVDF indicates that in both cases, no hydrophobic modifying compound is introduced, so the water molecules bound to the OMS are not replaced by surrounding water molecules. This means that, in the case of the catalyst complex according to the present invention, when the hydrogen isotope exchange reaction is carried out, the hydrophobic modification allows for the smooth replacement of existing water molecules with new water molecules in the new OMS, and this repeated adsorption and desorption supports the fact that the efficiency of the hydrogen isotope reaction is very high. In conclusion, in the case of Example 1, as shown in Figure 24, water molecules in the OMS are easily adsorbed and desorbed, and the reaction efficiency of the hydrogen isotope exchange is excellent.

[0188] Also, referring to Figure 23c, 2190 cm -1 , 2457cm -1 It can be seen that the peak has also increased, but this is a peak that was not observed in Figure 25 and is due to the bonding of platinum and D2O. Considering that the amount of platinum is only trace compared to OMS as shown in Table 2 above (molar ratio of Pt to Cr: 0.019), the peak intensity as shown in Figure 23c means that D2O is adsorbed to platinum very efficiently, which means that there is a very abundant amount of D2O available to participate in the reaction in Example 1. Furthermore, when this is compared with Figure 23d, such a peak is not observed in Pt@MIL-101 / PVDF in Figure 23d, so it can be said that the hydrophobic modification in Example 1 significantly increased the contact between platinum and D2O, which means that Example 1 is far superior to the other cases in terms of the efficiency of the hydrogen isotope exchange reaction.

[0189] <Experimental Example 18 - Structural Stability Analysis in a Radioactive Environment - SEM Analysis> Tritium emits radiation, which is different from deuterium. Therefore, in order to analyze the structural stability in a radioactive environment, after irradiating Example 1 with radiation, SEM images were taken and its structural stability was analyzed. At this time, analysis was performed for the case without irradiation with radiation and for the cases where the cumulative radiation dose reached 1 MGy and 3 MGy respectively at room temperature using an electron beam (1.2 MeV, beam current: 15 mA) and a film dosimeter (B3000). SEM photographs were taken and shown in Fig. 26.

[0190] As can be seen from Fig. 26, even after radioactive exposure, the porous PVDF matrix integrity is maintained in Example 1, and the Pt@MIL-101-12 dispersed inside has an octahedral crystal form, and it can be confirmed that the structural stability is maintained even in a radioactive environment. This means that the catalyst composite according to the present invention can operate even in an environment where tritium is present, and can exhibit excellent reaction efficiency even when the hydrogen isotope is tritium in the hydrogen isotope exchange reaction.

[0191] <Experimental Example 19 - Analysis of Structural Stability in Radioactive Environment - FT-IR Analysis> After irradiating Example 1 and Comparative Example 2 with radiation in the same manner as in Experimental Example 18, FT-IR analysis was performed, and the results are shown in Fig. 27.

[0192] As can be seen from Fig. 27, in both Example 1 and Comparative Example 2, peaks corresponding to 500 - 1700 cm -1 were observed before and after radioactive exposure, and the peaks at 2960 cm -1 and 2850 cm -1 due to the C-H stretching of dodecylamine were also maintained. Also, at both before and after radioactive exposure, about 1170, 1070, 880 and 840 cm -1Peaks were also observed. This means that both Example 1 and Comparative Example 2 maintained stability in their chemical bonds despite radiation exposure. This implies that the catalyst complex according to the present invention can operate even in an environment where tritium is present, and can exhibit excellent reaction efficiency even when the hydrogen isotope in the hydrogen isotope exchange reaction is tritium.

[0193] <Experimental Example 20 - Structural Stability Analysis in a Radioactive Environment - XRD Analysis> After irradiating Example 1 and Comparative Example 2 with radiation in the same manner as in Experimental Example 18, XRD analysis was performed, and the results are shown in FIG. 28.

[0194] As can be seen from FIG. 28, the XRD patterns are identical before and after irradiating Example 1 and Comparative Example 2 with radiation. This means that both Example 1 and Example 2 maintained a stable crystal structure despite the same radiation. This implies that the catalyst complex according to the present invention can operate even in an environment where tritium is present, and can exhibit excellent reaction efficiency even when the hydrogen isotope in the hydrogen isotope exchange reaction is tritium.

[0195] <Experimental Example 21 - Structural Stability Analysis in a Radioactive Environment - XPS Analysis> After irradiating Example 1 and Comparative Example 2 with radiation in the same manner as in Experimental Example 18, XPS analysis was performed, and the results are shown in FIG. 29.

[0196] As can be seen from FIG. 29, it can be confirmed that the spectra of Pt4f do not change on the XPS spectra of both Example 1 and Comparative Example 2 before and after radiation irradiation. This means that even after radiation irradiation, the oxidation state of Pt utilized in the catalyst does not change, and Pt remains in a state with catalytic activity even after radiation irradiation. This implies that the catalyst complex according to the present invention can operate even in an environment where tritium is present, and can exhibit excellent reaction efficiency even when the hydrogen isotope in the hydrogen isotope exchange reaction is tritium.

Claims

1. Catalyst support comprising a metal-organic structure composite having an open metal site (OMS) and pores; Hydrophobic modifying compound introduced into the aforementioned OMS (open metal site); and A hydrogen isotope exchange catalyst complex comprising a hydrogen isotope exchange metal catalyst introduced into the aforementioned pores.

2. The hydrogen isotope exchange catalyst complex further comprises a catalyst matrix, The catalyst complex for hydrogen isotope exchange according to claim 1, characterized in that the catalyst support is dispersed inside the catalyst matrix.

3. The hydrogen isotope exchange catalyst complex according to claim 1, characterized in that the water contact angle of the metal-organic structure complex is 90° or more.

4. The water contact angle of the metal-organic structure composite is 90° or more, and the water vapor diffusivity is 5 x 10⁻¹⁰. －１４ cm ２ The hydrogen isotope exchange catalyst complex according to claim 1, characterized in that it is 1 / s or greater.

5. The hydrogen isotope exchange catalyst complex according to claim 1, characterized in that the hydrophobic modifying compound is a compound represented by chemical formula 1. <Chemical formula 1> 【Chemistry 1】 At this time, the functional group (Fn) is -NH ２ , -NH-, -NRH, -N=, -NR ２ , -C ５ H ５ N, -OH, -COOH, -PH ２ , -PO ３ ２－ , any one of -SH, The aforementioned R １ This is one of the following: a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C1-C20 aryl group, and a C1-C20 heteroaryl group.

6. The hydrogen isotope exchange catalyst complex according to claim 1, characterized in that the hydrophobic modifying compound comprises one or more selected from the group consisting of dodecylamine, decylamine, octylamine, hexylamine, aniline, and benzylamine.

7. The hydrogen isotope exchange catalyst complex according to claim 1, characterized in that the hydrogen isotope exchange metal catalyst comprises one or more selected from the group consisting of Pt, Pd, Ir, Rh, Re, Ni, Co, W, Cu, Au, Ag, Mo, and Fe.

8. The catalyst complex for hydrogen isotope exchange according to claim 2, characterized in that the catalyst matrix is ​​a hydrophobic polymer matrix.

9. The hydrogen isotope exchange catalyst complex further comprises a binder, The catalyst complex for hydrogen isotope exchange according to claim 1, characterized in that the catalyst support is bound together by the binder.

10. (1) A step of preparing a metal-organic structure (MOF) having an Open Metal Site (OMS) and pores; (2) The step of introducing a hydrophobic modifying compound into the OMS of the metal-organic structure to form a hydrophobic modified metal-organic structure composite; and (3) The step of reacting the hydrophobic modified metal-organic structure composite with a catalyst matrix and dispersing it inside the catalyst matrix; A method for producing a hydrogen isotope exchange catalyst composite, comprising the step of introducing a hydrogen isotope exchange metal catalyst into the pores between step (1) and step (2) or between step (2) and step (3).

11. The method for producing a hydrogen isotope exchange catalyst composite according to claim 10, characterized in that the water contact angle of the hydrophobic modified metal-organic structure composite is 90° or more.

12. The method for producing a hydrogen isotope exchange catalyst complex according to claim 10, characterized in that the hydrophobic modifying compound is a compound represented by chemical formula 1. <Chemical formula 1> 【Chemistry 1】 In this case, the functional group (Fn) is -NH ２ , -NH-, -NRH, -N=, -NR ２ , -C ５ H ５ N, -OH, -COOH, -PH ２ , -PO ３ ２－ It is one of the following: , -SH The aforementioned R １ This is one of the following: a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C1-C20 aryl group, and a C1-C20 heteroaryl group.

13. A catalyst complex for hydrogen isotope exchange produced by the method described in any one of claims 10 to 12.

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