Catalyst loaded body, catalyst for vapor-phase oxidation of organic compound using same, and vapor-phase oxidation method

Abstract

[Problem] The present invention provides a means which is capable of oxidizing an organic compound in a vapor phase using a nitroxyl radical as a catalyst. [Solution] A catalyst loaded body is obtained by loading a carrier with a compound that has an oxidation-reduction mechanism described below together with a promoter that contains a transition metal. In the formula, X- represents a counter anion; and the broken line represents a bonding position with another atom.

Description

Catalyst support, catalyst for vapor-phase oxidation of organic compounds using the same, and vapor-phase oxidation method

[0001] The present invention relates to a catalyst support, a catalyst for the gas-phase oxidation of organic compounds using the same, and a gas-phase oxidation method.

[0002] Nitroxyl radicals are stable organic free radical molecules and are widely used as oxidation catalysts in organic synthesis. Organic nitroxyl radicals exhibit bidirectional reactivity, undergoing one-electron reduction to produce hydroxylamine and one-electron oxidation to produce oxoammonium ions, as shown in the following reaction schemes.

[0003]

[0004] The oxoammonium ion generated by the oxidation of nitroxyl radicals has strong oxidizing power and produces hydroxyamine after two-electron oxidation of the substrate. In oxidation reactions in which oxoammonium ions act as the active oxidizing species, a reactant that promotes the reoxidation of this hydroxyamine can be added to regenerate the oxoammonium ion, completing the catalytic cycle.

[0005] 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) has been known as such an oxidation catalyst. 2-Azaadamantane-N-oxyl (AZADO) has also been proposed as a catalyst that overcomes the large steric hindrance of TEMPO (see International Publication No. 2006 / 001387). AZADO has enabled highly efficient oxidation of a variety of alcohols with large steric hindrance to the corresponding carbonyl compounds.

[0006] On the other hand, in recent years, oxidation reactions using oxygen in the air as an oxidant have attracted much attention from the viewpoint of reducing environmental load. For example, Iwabuchi et al. ２ / O ２have reported that this reaction system can efficiently promote the oxidation of various alcohols (see M. Shibuya, Y. Osada, Y. Sasano, M. Tomizawa, Y. Iwabuchi, J. Am. Chem. Soc. 2011, 133, 6497-6500).

[0007] The techniques described in the above-mentioned WO 2006 / 001387 pamphlet and M. Shibuya, Y. Osada, Y. Sasano, M. Tomizawa, Y. Iwabuchi, J. Am. Chem. Soc. 2011, 133, 6497-6500 all involve oxidizing an alcohol to the corresponding aldehyde or ketone in a liquid phase system, and no technique has been reported to date for oxidizing an alcohol in a gas phase using a nitroxyl radical such as TEMPO or AZADO as a catalyst.

[0008] In the case of the reaction in a liquid phase system described in the above-mentioned document, it is necessary to separate the target product and catalyst from the solvent after the reaction is completed, and further purify the target product, which is problematic in terms of time and cost.

[0009] Therefore, an object of the present invention is to provide a technology that can oxidize organic compounds in the gas phase using nitroxyl radicals as a catalyst.

[0010] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved by a catalyst support in which a compound having the oxidation-reduction mechanism shown in the above reaction formula is supported on a support together with a co-catalyst, thereby completing the present invention.

[0011] That is, one aspect of the present invention is a catalyst support comprising a support on which a compound having the following oxidation-reduction mechanism and a co-catalyst containing a transition metal are supported:

[0012]

[0013] In the formula, X － is a counter anion, and the dashed lines represent the bond positions to other atoms.

[0014] According to the present invention, it is possible to oxidize organic compounds in the gas phase using nitroxyl radicals as a catalyst.

[0015] Figure 1 shows the standard redox potential (E ) between the nitroxyl radical form and the oxoammonium form for four compounds: (a) TEMPO, (b) AZADO, (c) 1-methyl AZADO, and (d) 1,3-dimethyl AZADO, measured by cyclic voltammetry. ０ FIG. 2 is an XRD pattern showing the results of XRD measurement of AZADO / GMS prepared in the examples, together with the measurement results for AZADO and GMS. FIG. 3 is an ESR spectrum showing the results of ESR measurement of AZADO / GMS prepared in the examples. FIG. 4 is a graph showing the results of a batch system vapor phase oxidation reaction of 2-propanol at 80°C using AZADO / GMS prepared in the examples as a catalyst (amount of acetone produced 24 hours after the start of the reaction), together with the results when GMS alone was used as a catalyst and when no catalyst was used (blank). FIG. 5 is a graph showing the results of the AZADO-Cu(NO ３ ) ２ / GMS, AZADO-CuI / GMS and AZADO-Fe(NO ３ ) ３ 6 is an XRD pattern showing the results of XRD measurement of AZADO-Cu(NO ３ ) ２ The results of XRD measurement of / GMS were compared with Cu(NO ３ ) ２ ・3H ２ O and Cu ２ (NO ３ ) (OH) ３ 7 shows the XRD pattern of AZADO-Cu(NO ３ ) ２ / GMS,Cu(NO ３ ) ２8 is a graph showing the results of a batch system gas phase oxidation reaction of 2-propanol using AZADO-Cu(NO) / GMS and AZADO / GMS as catalysts (amount of acetone produced 24 hours after the start of the reaction at 80°C), along with the results when only GMS was used as a catalyst. ３ ) ２ 9 is a graph showing the change in TON (Turnover Number) over time as an index of catalytic activity, showing the results of applying AZADO-Cu(NO) / GMS and AZADO-CuI / GMS as catalysts to the gas-phase oxidation reaction of 2-propanol at room temperature (30°C) in a batch system. ３ ) ２ / GMS was used as a catalyst, and the mixture was stirred at room temperature (24°C) in a flow system (containing 1.0 mmol / L of 2-propanol). ２ FIG. 10 is a graph showing the results of a gas-phase oxidation reaction of 2-propanol (flowing 20 mL / min) as a batch system using AZADO-Cu(bpy) / GMS as a catalyst (30°C) (change in TOF over time), as an index of catalytic activity. ３ ) ２ 11 is a graph showing the results of using AZADO-Cu(bpy) / GMS, AZADO-CuI / GMS, or AZADO / GMS as a catalyst. FIG. 11 is a graph showing the results of using AZADO-Cu(bpy) / GMS prepared in the examples as a catalyst in a flow system at 30° C. (O containing 1.8 mmol / L of 2-propanol). ２FIG. 12 is a graph showing the change in TOF over time when the gas-phase oxidation reaction of 2-propanol was carried out in a batch system at 30°C using AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS prepared in the examples as catalysts. FIG. 13 is a graph showing the change in TOF over time when the gas-phase oxidation reaction of ethanol was carried out in a batch system at 30°C using AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS prepared in the examples as catalysts. FIG. 14 is a graph showing the change in TOF over time when the gas-phase oxidation reaction of 2-propanol was carried out in a batch system at 30°C using AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS prepared in the examples as catalysts. ２ was introduced, and the reaction was carried out in a batch system at 30°C for 8 hours using AZADO-Cu(bpy) / GMS as a catalyst. The TON at 8 hours after the start of the reaction was ２ 15 shows the change in TON over time when a batch reaction was carried out at 30°C for 24 hours using AZADO-Cu(bpy) / GMS as a catalyst, with synthetic air containing 2-propanol at 1.8 mmol / L introduced into the reaction vessel. ２FIG. 16 is a graph showing the change over time in TON obtained for catalysts using various carbon materials as supports when a gas-phase oxidation reaction of 2-propanol was carried out in a batch system using catalysts in which AZADO and Cu(bpy) were supported on various carbon materials and oxides. FIG. 17 is a graph showing the change over time in TON obtained for catalysts using various oxides as supports when a gas-phase oxidation reaction of 2-propanol was carried out in a batch system using catalysts in which AZADO and Cu(bpy) were supported on various carbon materials and oxides. FIG. 18 is a scatter plot in which TON is plotted against the specific surface area, total pore volume, edge amount, and spin density of each carbon material 24 hours after the start of the reaction, obtained using catalysts supported on various carbon materials. Fig. 19 is a scatter diagram in which the TONs obtained 24 hours after the start of the reaction using catalysts with various oxide supports are arranged by the specific surface area of ​​each oxide, and the TONs 24 hours after the start of the reaction are plotted against the specific surface area of ​​each oxide support for the purpose of comparison with the case where a carbon support is used. Fig. 19 also shows plots for the cases where various carbon supports are used.

[0016] Hereinafter, embodiments of the present invention will be described.

[0017] <<Catalyst Supported Body>> One aspect of the present invention is a catalyst supported body in which a compound having the above-described oxidation-reduction mechanism (hereinafter also referred to as "the compound of this aspect") and a co-catalyst containing a transition metal (hereinafter also referred to as "the co-catalyst of this aspect") are supported on a support (hereinafter also referred to as "the support of this aspect").

[0018] <Compound of the Present Form> The compound of the present form may be any compound having the above-mentioned oxidation-reduction mechanism, and there is no limitation on its specific structure. Furthermore, when the compound of the present form is supported on a carrier, it may be in the hydroxylamine form, the nitroxyl radical form, or the oxoammonium form in the above-mentioned oxidation-reduction mechanism. Among these, the hydroxylamine form or the nitroxyl radical form is preferred, and the nitroxyl radical form is particularly preferred.

[0019] In addition, from the viewpoint of exhibiting excellent catalytic activity when used as an oxidation catalyst described later, the standard oxidation-reduction potential (25°C) between the nitroxyl radical form and the oxoammonium form of the compound of this embodiment is preferably +100 mV to +1000 mV [Ag / Ag ＋ ], and more preferably +130 mV to +600 mV [Ag / Ag ＋ The standard oxidation-reduction potential is measured by cyclic voltammetry (CV) at a temperature of 25°C. In this case, a glassy carbon electrode (inner diameter 3 mm) is used as a working electrode, and a reference electrode (Ag / Ag ＋ The measurement is performed in a three-electrode system using a first electrode (anode) and a counter electrode (platinum wire), with a potential sweep rate of 50 mV / s. Note that the hydroxylamine form of this compound is generally unstable and is rapidly oxidized to the nitroxyl radical form. Therefore, the standard redox potential measured by the above method is a value between the nitroxyl radical form and the oxoammonium form.

[0020] Here, for the four compounds of this embodiment, (a) TEMPO, (b) AZADO, (c) 1-methyl AZADO, and (d) 1,3-dimethyl AZADO, the standard oxidation-reduction potential (E ０ The cyclic voltammograms obtained by measuring the E of these compounds are shown in Figure 1. ０ The values ​​of (d) 136 mV < (c) 186 mV < (b) 236 mV < (a) 294 mV, respectively. The cyclic voltammogram shown in Figure 1 remained stable even after 100 or more cycles of measurement, which indicates that the compound of this embodiment has extremely high durability as an oxidizing agent.

[0021] From the viewpoint of catalytic activity, the compound of this embodiment preferably has a nitroxyl radical form represented by the following chemical formula 1.

[0022]

[0023] In Chemical Formula 1, R １ ~R ４ , Y １ and Y ２ are each independently a hydrogen atom or an optionally substituted monovalent organic group. The monovalent organic group is not particularly limited, but examples thereof include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heteroaryl group. １ ~R ４ , Y １ and Y ２ may be the same or different.

[0024] The alkyl group, alkenyl group, and alkynyl group as the monovalent organic group may each be linear, branched, or cyclic, but are preferably linear. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4. The number of carbon atoms in the alkenyl group and alkynyl group is not particularly limited, but is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 4.

[0025] The aryl group as a monovalent organic group is a group derived from a hydrocarbon ring having aromaticity in part or as a whole. When the aryl group contains two or more hydrocarbon rings having aromaticity in part or as a whole, these rings may be bonded to each other by a single bond or fused together. Furthermore, when the aryl group contains two or more hydrocarbon rings having aromaticity in part or as a whole, one atom may serve as a ring-forming atom of any two of these rings to form a spiro ring. The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 30. The number of carbon atoms in the aryl group is more preferably 6 to 12, and even more preferably 6. In particular, the aryl group is preferably a monovalent group derived from an aromatic hydrocarbon ring having 6 or more ring-forming atoms.

[0026] The heteroaryl group as a monovalent organic group is a group derived from a heterocycle having aromaticity in part or as a whole. When the heteroaryl group contains two or more heterocycles having aromaticity in part or as a whole, some or all of these rings may be bonded to each other via single bonds. When the heteroaryl group contains two or more heterocycles having aromaticity in part or as a whole, or other rings, these rings may be fused to each other. Furthermore, when the heteroaryl group contains two or more heterocycles having aromaticity in part or as a whole, or other rings, one atom may also serve as a ring-forming atom of these rings. The heteroatom contained in the heteroaryl group is not particularly limited, and examples thereof include one or more heteroatoms (e.g., nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom (S), silicon atom (Si), selenium atom (Se), germanium atom (Ge)) as ring-forming atoms. The number of carbon atoms in the heteroaryl group is preferably 3 to 30. Furthermore, the number of ring-forming atoms in the heteroaryl group is not particularly limited, but is preferably 5 to 30. Furthermore, the number of ring atoms in the heteroaryl group is more preferably 5 to 14, and even more preferably 5 to 13. The number of heteroatoms in the heteroaryl group is not particularly limited, but is preferably 1 to 3. The number of heteroatoms in the heteroaryl group is more preferably 1 to 2, and even more preferably 1. In particular, the heteroaryl group is preferably a monovalent group derived from an aromatic heterocycle having 5 or more ring atoms.

[0027] The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group as monovalent organic groups may each be a substituted group. The substituent is not particularly limited, but examples thereof include alkyl groups, alkoxy groups, alkenyl groups, alkynyl groups, halogen atoms, hydroxy groups, carboxy groups, cyano groups, amino groups, and carbamoyl groups. Among these, alkyl groups or halogen atoms are preferred as the substituent, and methyl groups, ethyl groups, or fluorine atoms are more preferred. Furthermore, methyl groups or fluorine atoms are even more preferred as the substituent. The above-mentioned substituents do not substitute the same type of group. For example, the substituents substituting alkyl groups do not include alkyl groups.

[0028] In addition, in Chemical Formula 1, from the viewpoint of excellent catalytic activity, Y １ and Y ２ are bonded to each other to form an optionally substituted nitrogen-containing monocyclo ring including a 5-membered or 6-membered ring, or further R １ and R ３ are bonded to each other to form a nitrogen-containing bicyclo ring containing a 5- or 6-membered ring which may be substituted, or two rings constituting the nitrogen-containing bicyclo ring are further crosslinked to form a nitrogen-containing tricyclo ring containing a 5- or 6-membered ring which may be substituted. That is, in a preferred embodiment of this aspect, the nitroxyl radical form of the compound of this aspect is represented by the following chemical formula 2.

[0029]

[0030] In Chemical Formula 2, R １ ~R ４ are each independently a hydrogen atom or an optionally substituted monovalent organic group, Z is an optionally substituted nitrogen-containing monocyclo ring containing a 5-membered or 6-membered ring, and in this case, R １ and R ３may be bonded to each other to form an optionally substituted nitrogen-containing bicyclo ring containing a 5- or 6-membered ring, or two rings constituting the nitrogen-containing bicyclo ring may be further bridged to form an optionally substituted nitrogen-containing tricyclo ring containing a 5- or 6-membered ring.

[0031] Examples of nitrogen-containing monocyclo rings as Z include aliphatic heterocycles such as a pyrrolidine ring, a piperidine ring, a morpholine ring, and a pyrroline ring, and aromatic heterocycles such as a pyrrole ring and an imidazole ring. １ and R ３ Examples of nitrogen-containing bicyclo rings formed by bonding together include a 9-azabicyclo[3.3.1]nonane ring and a 9-aza-3-oxabicyclo[3.3.1]nonane ring. Examples of nitrogen-containing tricyclo rings formed by further crosslinking two rings constituting the nitrogen-containing bicyclo ring include a 2-azaadamantane ring, a 2,6-diazaadamantane ring, a 6-aza-2-oxaadamantane ring, and a 9-aza-6-noradamantane ring. Among these, from the viewpoint of excellent catalytic activity, the compound of this embodiment preferably has a nitrogen-containing monocyclo ring, a nitrogen-containing bicyclo ring, or a nitrogen-containing tricyclo ring, more preferably a nitrogen-containing monocyclo ring or a nitrogen-containing tricyclo ring, and particularly preferably a nitrogen-containing tricyclo ring. Furthermore, the compound of this embodiment preferably has an aliphatic heterocycle which is a nitrogen-containing monocyclo ring or a 2-azaadamantane ring or a 9-aza-6-noradamantane ring which is a nitrogen-containing tricyclo ring, and more preferably has a piperidine ring which is a nitrogen-containing monocyclo ring or a 2-azaadamantane ring which is a nitrogen-containing tricyclo ring.

[0032] The nitrogen-containing monocyclo ring formed in Chemical Formula 2, or the nitrogen-containing bicyclo ring or nitrogen-containing tricyclo ring that can be formed in Chemical Formula 2, is an optionally substituted ring structure. Substituents that can substitute these ring structures are not particularly limited, and examples include alkyl groups, alkoxy groups, alkenyl groups, alkynyl groups, halogen atoms, hydroxy groups, carboxy groups, carbonyl groups, cyano groups, amino groups, carbamoyl groups, tosyl groups, (halogenated) acylamino groups, and phosphate groups. Among these, methyl groups, ethyl groups, methoxy groups, ethoxy groups, fluorine atoms, hydroxy groups, carboxy groups, and tosyl groups are more preferred as the substituent.

[0033] Here, when the compound of this embodiment does not contain the above ring structure or contains a nitrogen-containing monocyclo ring, R １ ~R ４ are each independently preferably a hydrogen atom or an optionally substituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group, even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group. From the viewpoint of catalytic activity, when the compound of this embodiment contains the nitrogen-containing bicyclo ring or nitrogen-containing tricyclo ring, R ２ and R ４ are each independently preferably a hydrogen atom or an optionally substituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group, even more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0034] Examples of compounds of this embodiment are as follows (shown in nitroxyl radical form). Note that for some compounds, the standard oxidation-reduction potential (25°C) between the above-mentioned nitroxyl radical form and oxoammonium form is also shown. In view of the mechanism by which the catalyst support according to this embodiment exhibits excellent catalytic activity, all of the compounds shown below can be said to exhibit high catalytic activity.

[0035]

[0036]

[0037]

[0038] The above-mentioned E ０ In view of the value of , when a heteroatom is introduced into the structure of TEMPO, ABNO, AZADO, etc. that constitutes the skeleton of the compound, the redox characteristics of the compound in this form shift to the higher potential side. From this, it is thought that the oxidizing power as the potential of the corresponding oxoammonium form increases.

[0039] Among the above compounds, from the viewpoint of catalytic activity, preferred are TEMPO, 4-hydroxy TEMPO, 4-methoxy TEMPO, 4-acetylamino TEMPO, 4-oxo TEMPO, 4-carboxy TEMPO, 4-amino TEMPO, 4-phosphono TEMPO, 4-(2-bromoacetamido) TEMPO, AZADO, 1-methyl AZADO, 1,3-dimethyl AZADO, 1-fluoro AZADO, and 5-methyl AZADO. 5,7-difluoroAZADO, 5-fluoro-1-methylAZADO, 5,7-difluoro-1-methylAZADO, 5-methoxyAZADO, 5-methoxy-1-methylAZADO, 5,7-dimethoxyAZADO, oxa-AZADO, TsN-AZADO, diAZADO or Nor-AZADO, more preferably AZADO, 1-methylAZADO, 1,3-dimethylAZADO AZADO, 1-fluoroAZADO, 5-fluoroAZADO, 5,7-difluoroAZADO, 5-fluoro-1-methylAZADO, 5,7-difluoro-1-methylAZADO, 5-methoxyAZADO, 5-methoxy-1-methylAZADO, 5,7-dimethoxyAZADO, oxa-AZADO, TsN-AZADO, diAZADO or Nor-AZADO, and more preferably AZADO, 1 1-methyl AZADO, 1,3-dimethyl AZADO, 1-fluoro AZADO, 5-fluoro AZADO, 5,7-difluoro AZADO, 5-fluoro-1-methyl AZADO, 5,7-difluoro-1-methyl AZADO, 5-methoxy AZADO, 5-methoxy-1-methyl AZADO, and 5,7-dimethoxy AZADO are particularly preferred, and AZADO (2-azaadamantane-N-oxyl) is particularly preferred.

[0040] <Co-catalyst of this embodiment> In the catalyst support of this embodiment, the above-mentioned compound is supported on a carrier together with the co-catalyst. Here, the co-catalyst of this embodiment contains a transition metal. The co-catalyst may be in the form of a simple transition metal or a transition metal compound (e.g., a salt or complex). The transition metal that can be contained in the co-catalyst of this embodiment is not particularly limited as long as it is a metal element classified as an element of Group 3 to Group 12 of the periodic table. In particular, from the viewpoint of excellent catalytic activity, the transition metal preferably contains one or more selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn, and Cu, and more preferably contains ions (salts) of these metals. Furthermore, the transition metal more preferably contains Cu, particularly preferably contains Cu ions (salts), and most preferably contains divalent Cu ions (Cu(II) ions). It has been reported that in a liquid phase reaction using AZADO as a catalyst, the use of Cu(I) ions results in higher activity than the use of Cu(II) ions. In contrast, in a reaction using the catalyst support according to the present embodiment, it has been confirmed that a catalyst containing divalent Cu(II) ions exhibits higher activity than a catalyst containing monovalent Cu(I) ions.

[0041] When the co-catalyst contains a transition metal ion (salt), the counter anion of the ion is not particularly limited. Examples of salts containing a transition metal as a co-catalyst include sulfates, sulfites, hyposulfites, persulfates, thiosulfates, carbonates, phosphates, pyrophosphates, hydrochlorides, nitrates, nitrites, halides (e.g., fluorides, chlorides, bromides, iodides), and trifluoromethanesulfonates. However, as described above, it is preferable that the transition metal is contained in the form of a divalent ion.

[0042] Although there are no particular limitations on the amounts of the compound and the transition metal supported on the catalyst support of this embodiment, from the viewpoint of excellent catalytic activity, the molar ratio of the amounts of these components supported is preferably 1:2 to 4:1 (compound:transition metal), and more preferably 2:3 to 3:2. Furthermore, although details of the support will be described later, from the viewpoint of catalytic activity, the coverage of the surface area of ​​the support by the compound and the co-catalyst is preferably 10 to 300%. The value of the coverage can be determined by approximating the size of the compound and the co-catalyst (metal, ligand) according to this embodiment to a circle or rectangle, calculating the coverage of the support surface by each component, and adding up all the results. For example, in the case of AZADO-Cu(bpy), AZADO can be approximated to a size similar to that of cyclohexane (a square with one side measuring 5 Å), while Cu in Cu(bpy) can be approximated to a circle with a radius of 1.28 Å, and bpy can be approximated to a rectangle measuring 5 Å x 8.5 Å. Here, when the coverage value exceeds 100%, it is considered that a complete coverage layer of the above components is formed on the surface of the carrier, and then the above components are further laminated on top of the complete coverage layer. This coverage value can be controlled by adjusting the blending amounts of each component when producing the catalyst carrier.

[0043] The catalyst support of this embodiment must have the above-described compound and transition metal supported on the carrier, but other components may also be supported as needed. Examples of other components include ligands. Supporting a ligand can further improve catalytic activity. In this case, the transition metal and the ligand may form a complex. While conventionally known ligands can be used as appropriate, compounds containing a nitrogen-containing six-membered ring are preferred. Among these, pyridine ring-containing compounds are more preferred, and bipyridine compounds, terpyridine compounds, or phenanthroline compounds are even more preferred. Specific examples of these compounds include 2,2'-bipyridine (bpy), 2,6-di(2-pyridyl)pyridine, 1,10-phenanthroline, 4,7-biphenyl-1,10-phenanthroline, 1,7-phenanthroline, bathocuproine, and bathocuproine sulfonic acid. Of these, 2,2'-bipyridine (bpy) is particularly preferred. When a ligand is used, the amount of the ligand to be supported is not particularly limited. However, from the viewpoint of excellent catalytic activity, the molar ratio of the co-catalyst to the ligand is preferably 3:1 to 1:3 (co-catalyst:ligand), and more preferably 2:1 to 1:2.

[0044] <Support of the Present Embodiment> The specific configuration of the support of the present embodiment is not particularly limited, and conventionally known knowledge can be appropriately referred to. Examples of the support include metal oxides and carbon materials, with carbon materials being more preferred. Examples of metal oxides that can be used as the support include silica (silica gel, fumed silica, etc.), alumina (α-alumina, θ-alumina, γ-alumina, δ-alumina, β-alumina, etc.), titania, ceria, silica-alumina, zirconia, magnesia, and zeolite. When a metal oxide is used as the support, the metal oxide is preferably alumina, titania, or ceria, and more preferably alumina.

[0045] Furthermore, a preferred example of the carbon material used as a support is a porous carbon material. The porous carbon material is composed mainly of carbon. Here, "composed mainly of carbon" is a concept that includes both "consisting only of carbon" and "consisting essentially of carbon," and elements other than carbon may be included. "Consisting essentially of carbon" means that 80% by mass or more of the total, preferably 95% by mass or more of the total, and more preferably 98% by mass or more of the total (upper limit: 100% by mass) is composed of carbon.

[0046] The BET specific surface area of ​​the porous carbon material is not particularly limited, but it has surprisingly been found that the smaller the BET specific surface area of ​​the carrier of this embodiment, the more preferable it is. Specifically, the BET specific surface area of ​​the carrier is preferably 3000 m ２ / g or less, and more preferably 2000m ２ / g or less, and more preferably 1000m ２ / g or less, and particularly preferably 500m ２ On the other hand, there is no particular restriction on the lower limit of the BET specific surface area, but it is usually 10 m ２ / g or more, preferably 50m ２ / g or more, more preferably 60m ２ That is, in a preferred embodiment of this aspect, the carrier has a surface area of ​​50 to 3000 m ２ The porous carbon material has a BET specific surface area of ​​1 / g. By adopting such a configuration, it is possible to exhibit excellent catalytic activity. The BET specific surface area of ​​the porous carbon material can be determined by the BET method from the measurement results of the nitrogen adsorption / desorption isotherm.

[0047] Specific examples of porous carbon materials include graphene meso sponge (GMS), carbon meso sponge (CMS), activated carbon (YP-50F), zeolite-templated carbon (ZTC), Ketjen Black, Vulcan, and Denka Black (DB). Among these, Denka Black, Vulcan, Ketjen Black, or activated carbon is preferred as the porous carbon material, and Denka Black or Vulcan is more preferred. Regarding the production methods of CMS or GMS, known knowledge can be referred to as appropriate.

[0048] There are no particular limitations on the method for producing the catalyst supporter according to this embodiment, and a person skilled in the art can appropriately produce it by taking into consideration the common general knowledge in this technical field as well as the examples section described below.

[0049] <<Catalyst for Gas-Phase Oxidation of Organic Compounds>> The catalyst support according to one embodiment of the present invention described above is used, for example, for the gas-phase oxidation of organic compounds. That is, another embodiment of the present invention is a catalyst for the gas-phase oxidation of organic compounds, comprising the catalyst support according to one embodiment of the present invention described above. Conventionally, it has been proposed to oxidize alcohols in a liquid-phase system using the above-described compound as a catalyst. However, in the case of a reaction in a liquid-phase system, it is necessary to separate the target product and catalyst from the solvent after completion of the reaction, and further purify the target product, which poses problems in terms of time and cost. In contrast, the catalyst for gas-phase oxidation of organic compounds according to this embodiment enables the oxidation of organic compounds in a gas-phase system, and has the advantage of not encountering the above-mentioned problems associated with reactions in a liquid-phase system. The organic compounds to be oxidized by the gas-phase oxidation catalyst according to this embodiment will be described later.

[0050] <<Method for Gas-Phase Oxidation of Organic Compound>> According to yet another aspect of the present invention, there is also provided a method for gas-phase oxidation of an organic compound, which specifically comprises contacting an organic compound having an oxidizable functional group with the catalyst support according to one aspect of the present invention in a gas phase in the presence of molecular oxygen, thereby oxidizing the oxidizable functional group.

[0051] <Organic Compound> In the gas-phase oxidation method according to the present embodiment, the target to be oxidized is an organic compound having an oxidizable functional group. The oxidizable functional group is not particularly limited, but examples thereof include a hydroxyl group and a thiol group, and preferably a hydroxyl group. Furthermore, since the oxidation method according to the present embodiment is carried out in a gas-phase system, the organic compound is preferably a volatile organic compound (VOC). Examples of the organic compound include alcohols such as primary alcohols and secondary alcohols, and mercaptans. According to the gas-phase oxidation method according to the present embodiment, primary alcohols are oxidized to the corresponding aldehydes, secondary alcohols are oxidized to the corresponding ketones, and mercaptans are dimerized and oxidized to the corresponding disulfides. Among these, from the viewpoint of ease of reaction progression, the organic compound is preferably an alcohol, and more preferably a primary alcohol or a secondary alcohol.

[0052] <Reaction Conditions> The reaction conditions for carrying out the gas-phase oxidation method according to this embodiment are not particularly limited, except for the specific configuration, as long as the reaction is carried out in a gas phase in which molecular oxygen is present. The "gas phase in which molecular oxygen is present" can be achieved, for example, by supplying molecular oxygen into the reaction system. Pure oxygen gas may be used as a source of molecular oxygen, but the reaction can also be carried out using air or an oxygen-containing mixed gas diluted with an inert gas such as nitrogen gas or carbon dioxide gas to an oxygen content of approximately 5 to 50% by volume. The reaction system is not particularly limited and may be a closed system, a flow system, or an open system (in the atmosphere).

[0053] The reaction temperature can be constant or can be changed. When the reaction temperature is constant, the reaction temperature is not particularly limited, but is preferably 0°C or higher, more preferably 10°C or higher, even more preferably 15°C or higher, and particularly preferably 20°C or higher. A temperature of 0°C or higher can increase the reactivity of the oxidation reaction. On the other hand, the reaction temperature is preferably 100°C or lower, more preferably 80°C or lower, even more preferably 50°C or lower, and particularly preferably 40°C or lower. A reaction temperature of 100°C or lower can suppress deterioration of the catalyst support. Furthermore, when the reaction temperature is changed, the temperature can be increased or decreased, or the temperature can be increased and decreased repeatedly.

[0054] The reactor for the gas-phase oxidation reaction is not particularly limited as long as it can bring the target gas into contact with the catalyst support (gas-phase oxidation catalyst), and any of a flow reactor, a full-batch reactor, and a semi-batch reactor can be used. Examples of flow reactors include a fixed-bed atmospheric flow reactor and a fluidized-bed reactor. A fixed-bed atmospheric flow reactor uses a fixed bed in which the catalyst is formed into granules and fixed. A fluidized-bed reactor uses a moving bed in which the catalyst moves. From the viewpoint of efficiently bringing the reaction gas into contact with the catalyst, it is preferable to use a fixed-bed atmospheric flow reactor. In the reactors described above, the catalyst may be heated externally using an electric heater, infrared rays, or the like.

[0055] The gas-phase oxidation method of organic compounds using the above-described gas-phase oxidation catalyst is not limited to the above-described embodiment, and may be, for example, arranged in a wind direction louver installed in the outlet of an automobile air conditioner (air conditioner) or in a filter installed in front of the outlet. According to such an embodiment, organic compounds contained in air cooled or heated by the air conditioner and discharged from the outlet can be oxidized. The air discharged from the air conditioner may contain organic compounds (e.g., alcohol) with a distinctive odor. According to the above embodiment, this odor can be reduced by oxidizing such organic compounds.

[0056]

[0023] According to yet another aspect of the present invention, there is also provided a catalyst-containing substrate in which the catalyst support according to the aspect of the present invention is supported on or coated on a base substrate. By forming such a catalyst-containing substrate, the catalyst support can be easily used for various purposes.

[0057] Examples of the base substrate constituting the catalyst-containing substrate include inexpensive materials that can easily support or coat a catalyst carrier, such as woven fabric, nonwoven fabric, filter, or urethane foam. There are no particular limitations on the method for supporting or coating a catalyst carrier on these base substrates. Such catalyst-containing substrates can be suitably used for applications such as masks, medical textile products, air conditioners, air purifiers, freezers, temperature controllers, dehumidifiers, humidifiers, or suction vacuum cleaner filters. Of course, they may also be used for other applications.

[0058] In yet another aspect of the present invention, a spray is also provided. The spray includes a spray container and a solution in which the catalyst carrier is dispersed, the solution being contained in the spray container. When sprayed onto a desired location, the spray according to this aspect can oxidize organic compounds at the location, thereby achieving an effect of reducing the odor of the organic compounds, for example.

[0059] The following embodiments are also included within the scope of the present invention: a catalyst supporter according to claim 1 having the features of claim 2; a catalyst supporter according to claim 1 or 2 having the features of claim 3; a catalyst supporter according to any one of claims 1 to 3 having the features of claim 4; a catalyst supporter according to claim 3 or 4 having the features of claim 5; a catalyst supporter according to any one of claims 1 to 5 having the features of claim 6; a catalyst supporter according to any one of claims 1 to 6 having the features of claim 7; a catalyst supporter according to any one of claims 1 to 7 having the features of claim 8; a catalyst supporter according to any one of claims 1 to 8 having the features of claim 9; a catalyst supporter according to any one of claims 1 to 9 having the features of claim 10; a catalyst supporter according to any one of claims 1 to 9 having the features of claim 11 a catalyst for the gas-phase oxidation of organic compounds comprising the catalyst support according to any one of claims 1 to 12; a method for the gas-phase oxidation of organic compounds using the catalyst support according to any one of claims 1 to 12; a method according to claim 14 having the characteristics of claim 15; a method according to claim 14 or 15 having the characteristics of claim 16; a catalyst-containing substrate using the catalyst support according to any one of claims 1 to 12; a catalyst-containing substrate according to claim 17 having the characteristics of claim 18; a catalyst-containing substrate according to claim 17 or 18 having the characteristics of claim 19; a spray using the catalyst support according to any one of claims 1 to 12.

[0060] Hereinafter, the embodiments of the present invention will be described in detail using examples, but the technical scope of the present invention is not limited to the following examples.

[0061] Preparation Examples of Catalyst Supports (Preparation of AZADO / GMS, AZADOL / GMS, and NHPI / GMS) 5 mg (0.13 mmol) of AZADO and 100 mL of dichloromethane were added to a 300 mL eggplant-shaped flask, and the AZADO was dissolved by ultrasonic waves. ＢＥＴ = 1,692 m ２100 mg of 100 mg of 100% ethanol (100 mg / g) was added and dispersed ultrasonically for 30 minutes, followed by stirring at room temperature for 30 minutes. The mixture was then evaporated to dryness using a rotary evaporator at 40°C and 600 hPa, and then vacuum dried for 10 hours to obtain a catalyst support (AZADO / GMS). In addition to AZADO, catalyst supports (AZADOL / GMS and NHPI / GMS) were also prepared using 2-azaadamantane-N-hydroxyl (AZADOL), in which the nitroxyl radical of AZADO was replaced with an alcohol, and N-hydroxyphthalimide (NHPI), respectively.

[0062] (Preparation of AZADO-metal salt / GMS) Metal salt 0.13 mmol (CuI: 25.0 mg, Cu(NO ３ ) ２ ・3H ２ O: 31.7 mg, or Fe(NO ３ ) ３ ・9H ２ A 300-mL eggplant-shaped flask was charged with 200 mL of water / ethanol (50% by volume each, or 200 mL of acetonitrile when CuI was used as the metal salt) and the metal salt was dissolved using ultrasound. 400 mg of GMS (the carrier) was added and dispersed using ultrasound for 30 minutes, followed by stirring at room temperature for 30 minutes. The mixture was then evaporated to dryness using a rotary evaporator at 60°C and 100 hPa (60°C and 250 hPa when acetonitrile was used as the impregnation solution), and further dried in vacuum for 10 hours to obtain metal salt-supported GMS.

[0063] Next, 5 mg (0.0328 mmol) of AZADO and 100 mL of dichloromethane were added to a 300 mL eggplant-shaped flask, and the AZADO was dissolved by ultrasonic waves. The metal salt-supported GMS prepared in advance was added so that the amount of each metal ion was equal to the amount of AZADO (CuI / GMS: 102.2 mg, Cu(NO ３ ) ２ / GMS: 102.5 mg, Fe(NO ３ ) ３The mixture was dispersed by ultrasonic waves for 30 minutes and then stirred at room temperature for 30 minutes. The mixture was then evaporated to dryness using a rotary evaporator at 40°C and 600 hPa, and further dried in vacuum for 10 hours to obtain catalyst supports (AZADO-CuI / GMS, AZADO-Cu(NO)). ３ ) ２ / GMS and AZADO-Fe(NO ３ ) ３ / GMS) was obtained.

[0064] (Preparation of AZADO-Cu(bpy) / GMS) Cu(OTf) ２ 0.03 mmol (10.9 mg), 0.03 mmol (4.7 mg) of bpy, and 0.03 mmol (4.6 mg) of AZADO were each added to a 5 mL vial, dissolved in 3 mL of acetonitrile, and added to a 300 mL eggplant-shaped flask containing 90 mL of acetonitrile. After adding each reagent, the vial walls were washed with acetonitrile and added to the flask. Next, 100 mg of the carrier, GMS, was added to the flask, dispersed ultrasonically for 30 minutes, and then stirred at room temperature for 30 minutes. The mixture was then evaporated to dryness using a rotary evaporator at 60 °C and 250 hPa, and further dried in vacuum for 10 hours to obtain a catalyst support (AZADO-Cu(bpy) / GMS) in which the cocatalyst was supported together with AZADO. The coverage of the catalyst support obtained in this manner was 8%.

[0065] (Preparation of AZADO-Cu(bpy) catalyst support using various carbon materials and oxides as supports) Catalyst supports were prepared using the same procedure as in the above "Preparation of AZADO-Cu(bpy) / GMS". As the support, activated carbon (YP-50F, S) was used in addition to GMS. ＢＥＴ = 1,700 m ２ / g), Zeolite Templated Carbon (ZTC, S ＢＥＴ = 3,790 m ２ / g), carbon meso sponge (CMS, S ＢＥＴ = 2,150 m ２ / g), Ketjen Black (registered trademark) EC300J (Ketjen Black, KB, S ＢＥＴ = 800m ２ / g), Vulcan® XC-72 (VC, S ＢＥＴ = 220 m ２ / g), and Denka Black (registered trademark) (Denka Black, DB, S ＢＥＴ = 68 m ２ / g), and silica gel (Wakosil (registered trademark) C-300, S ＢＥＴ = 475 m ２ / g), fumed silica (S ＢＥＴ = 395 m ２ / g), aluminum oxide (TM-100, S ＢＥＴ = 120 m ２ / g), titanium oxide (S ＢＥＴ = 46 m ２ / g), magnesium oxide (S ＢＥＴ = 60m ２ / g), cerium oxide (S ＢＥＴ =70m ２ / g) and zeolite (HSZ-320NAA, S ＢＥＴ = 660 m ２ / g) were used. The coverage of the catalyst support thus obtained was 8% (YP-50F), 2% (ZTC), 6% (CMS), 16% (KB), 60% (VC), 193% (DB), 28% (silica gel), 33% (fumed silica), 109% (aluminum oxide), 285% (titanium oxide), 219% (magnesium oxide), 187% (cerium oxide), and 20% (zeolite).

[0066] <<Evaluation of Physical Properties of Catalyst Support>> [Structural Analysis of AZADO / GMS and Evaluation of Catalytic Activity] (Structural Analysis of AZADO / GMS) - XRD Measurement XRD measurement was performed on the AZADO / GMS prepared above to analyze the catalyst structure. Similar measurements were also performed on GMS and AZADO. A Rigaku MiniFlex 600 was used as the measurement device, and CuKα radiation (1.5406 Å) was used as the X-ray source. The measurement was performed by spreading the sample evenly in a circular depression with a diameter of 5 mm on a Si non-reflective sample plate. The measurement conditions were as follows: X-ray tube: Cu, tube voltage: 40 kV, tube current: 15 mA, slits DS: 1.25 deg., RS: 13.0 mm, SS: 8.0 mm, measurement detector: D / tex Ultra, sampling width: 0.02 deg. Scan speed: 10.0 deg. / min. Scan axis: 2θ / θ. Measurement range: 2-60 deg. The obtained XRD patterns are shown in Figure 2. In the XRD pattern of GMS, peaks corresponding to carbon (002) and (10) were observed near 2θ = 26° and 44°, respectively. In addition, in the XRD pattern of AZADO, sharp peaks were observed near 16.2° and 18.7°. The XRD pattern obtained for AZADO / GMS was equivalent to that for GMS, indicating that AZADO was supported on GMS with high dispersion.

[0067] ESR measurement The AZADO / GMS (2% in Al) prepared above ２ O ３ The ESR measurement was performed on a 10 μM AZADO toluene solution and GMS (2% in Al) to analyze the state of AZADO on GMS. ２ O ３) was also measured in the same manner. The measurement apparatus used was a JEOL JES-X330. The powder catalyst sample was diluted 50-fold by mixing with alumina powder in an agate mortar, and 100 mg of this was filled into a quartz / Pyrex (registered trademark) sample tube with an inner diameter of 4 mm and a length of 180 mm for measurement. AZADO was dissolved in toluene to prepare a 10 μM toluene solution, and 600 μL was filled into the same sample tube as for the powder sample for measurement. The measurement conditions were as follows: Sweep magnetic field range: 336 ± 15 mT Sweep time: 1.0 min Microwave output: 1 mW Time constant: 0.03 s Modulation magnetic field frequency: 100 kHz Modulation magnetic field: 0.2 mT Amplification factor: 100 Mn marker insertion amount: 800 The resulting ESR spectrum is shown in Figure 3. In the ESR spectrum of the AZADO toluene solution, three peaks due to the unpaired electrons of AZADO were observed. Furthermore, the ESR spectrum of GMS diluted with alumina showed a weak peak due to the unpaired electron of GMS, and the ESR spectrum of AZADO / GMS diluted with alumina showed a peak that was thought to be a superposition of a signal due to AZADO and a signal due to GMS, suggesting that AZADO exists as a radical species on GMS.

[0068] (Evaluation of catalytic activity by vapor-phase oxidation reaction of 2-propanol in a batch system) Using the AZADO / GMS prepared above as a catalyst, a vapor-phase oxidation reaction of 2-propanol was carried out in a batch system at 80°C. Similar reactions were also carried out using only GMS as a catalyst and without a catalyst (blank). Here, 30 mg of AZADO / GMS and 20 mg of GMS were used. The amount of acetone produced 24 hours after the start of the reaction is shown in Figure 4. When AZADO / GMS was used as a catalyst, 0.43 μmol of acetone (0.29 μmol calculated based on 20 mg of catalyst) was produced 24 hours after the start of the reaction. The catalyst turnover number (TON) was calculated to be 0.05, indicating that the catalytic activity of AZADO / GMS was very low. When GMS was used as a catalyst and when no catalyst was used, the amounts of acetone produced 24 hours after the start of the reaction were 0.094 μmol and 0.11 μmol, respectively, indicating that GMS alone does not promote the gas-phase oxidation reaction of 2-propanol.

[0069] [AZADO-Cu(NO ３ ) ２ Structural analysis of / GMS and evaluation of catalytic activity] (AZADO-Cu(NO ３ ) ２ / GMS structural analysis) XRD measurement ３ ) ２ / GMS, AZADO-CuI / GMS and AZADO-Fe(NO ３ ) ３ XRD measurements were performed on AZADO-CuI / GMS to analyze the catalyst structure. The obtained XRD patterns are shown in Figure 5. ３ ) ３ With AZADO-Cu(NO) / GMS, a pattern equivalent to that with GMS was obtained, confirming that AZADO and the metal promoter were highly dispersed and supported on GMS. ３ ) ２ In the case of / GMS, peaks were observed around 12.7° and 25.6°. However, these peaks were not due to Cu(NO ３ ) ２ ・3H ２The peaks did not match those observed for Cu (Fig. 6). Therefore, the obtained XRD pattern was compared with a database, and these two peaks were found to be the same as those observed for Cu. ２ (NO ３ ) (OH) ３ (PDF#45-0594) (Fig. 6). ３ ) ２ / Cu on GMS ２ (NO ３ ) (OH) ３ was found to be formed.

[0070] Elemental analysis of the AZADO-Cu(NO ３ ) ２ The catalyst was subjected to CHN elemental analysis and ICP emission spectroscopy to analyze the contents of carbon (C), hydrogen (H), nitrogen (N), and copper (Cu). GMS was composed only of carbon, and the AZADO and Cu(NO) added during the catalyst preparation were added. ３ ) ２ It was assumed that all of the above were supported on GMS. The analytical equipment used for CHN elemental analysis was a MICRO CORDER JM10 manufactured by J Science Lab. The analytical conditions were as follows: Bridge current H: 91 mA C: 68 mA N: 125 mA Furnace temperature SF: 950°C CF: 830°C RF: 550°C Flow rate He: 180 mL / min O: 17 mL / min Combustion time: 240 seconds. The analytical equipment used for ICP optical emission spectroscopy was an inductively coupled plasma (ICP) optical emission spectroscopy analyzer (Hitachi High-Tech Science Corporation, SPS-3500 model).

[0071] As a result of the above analysis, it was found that about 67% of the added Cu was supported on GMS from the theoretical and measured values ​​of the content of each element calculated from the charged amount. Considering that the theoretical amount of N derived from AZADO is 0.4 wt%, it was found that the amount of nitrate ions (NO ３－ ) is Cu(NO ３ ) ２Assuming that the AZADO was supported on the GMS as a single layer, it was estimated that 100% of the added AZADO was supported on the GMS. ２ (NO ３ ) (OH) ３ It was inferred that the formation of

[0072] (Evaluation of catalytic activity) Vapor phase oxidation reaction of 2-propanol in a batch system. ３ ) ２ / GMS,Cu(NO ３ ) ２ Using AZADO / GMS and AZADO / GMS as catalysts, a batch system was used to carry out a gas-phase oxidation reaction of 2-propanol. Specifically, 20 mg of the catalyst support was weighed into a 100 mL reagent bottle and the bottle was capped with a screw cap designed for dehydrated solvents. Then, 20 mg of the catalyst support was weighed into a 100 mL reagent bottle and the bottle was capped with a screw cap designed for dehydrated solvents. ２ was introduced at a rate of 50 mL / min for 15 minutes, and the reagent bottle was placed in an incubator maintained at 30°C to carry out the reaction for 24 hours. When AZADO-Cu(bpy) / GMS was used as the catalyst, O ２ Instead of N ２ When AZADO / GMS was used as the catalyst, 20 mg of the catalyst was weighed into a 50 mL vial, which was then capped with a septum and wrapped in parafilm. ２ was introduced at 50 mL / min for 15 minutes, and the bottom of the vial was immersed in an oil bath at 80°C to carry out the reaction for 24 hours. ３ ) ２ When GMS is used as the catalyst, 20 mg of the catalyst is weighed into a 100 mL reagent bottle, and the bottle is closed with a screw cap designed for dehydrated solvents. Then, the bottle is filled with 0.7 mmol / L of 2-propanol. ２ was introduced at 50 mL / min for 15 minutes, and the bottom of the reagent bottle was immersed in an oil bath at 80°C or 30°C to carry out the reaction for 24 hours. ３ ) ２When GMS was used as the catalyst, the bubbler was not heated with an oil bath, and only the lower part of the reaction vessel was heated, not the entire vessel.

[0073] At the start of the reaction and after a certain period of time, 1 mL of reaction gas was collected using a gas-tight syringe and analyzed by gas chromatography. A flame ionization detector (FID) was used as the detector. The reaction conditions and analysis conditions were as follows: (Reaction conditions) Catalyst support 80°C: AZADO / GMS 30 mg: AZADO-Cu(NO ３ ) ２ / GMS,Cu(NO ３ ) ２ / GMS, AZADO / GMS, GMS 20 mg each 30°C: AZADO / GMS, AZADO-Cu (NO ３ ) ２ / GMS, AZADO-CuI / GMS, AZADO-Cu(bpy) / GMS, TEMPO-Cu(bpy) / GMS, AZADO-Cu(bpy) / YP-50F, AZADO-Cu(bpy) / ZTC, AZADO-Cu(bpy) / CMS , AZADO-Cu (bpy) / KB, AZADO-Cu (bpy) / VC, AZADO-Cu (bpy) / DB, AZA DO-Cu(bpy) / silica gel, AZADO-Cu(bpy) / fumed silica, AZADO-Cu(bpy) / Al ２ O ３ , AZADO-Cu(bpy) / TiO ２ , AZADO-Cu(bpy) / MgO, AZADO-Cu(bpy) / CeO ２ , AZADO-Cu(bpy) / zeolite 20 mg each Oxidizing agent O ２ Reaction substrate: 2-propanol Reaction temperature: Oil bath 80°C or 30°C Incubator 30°C (Analysis conditions)

[0074]

[0075] The amount of acetone produced 24 hours after the start of the reaction at 80°C is shown in Figure 7. When GMS and GMS carrying AZADO were used as catalysts, the progress of the oxidation reaction was hardly observed.３ ) ２ On the other hand, when AZADO and Cu(NO) were supported on GMS, a small amount of acetone was produced, at 2.6 μmol. ３ ) ２ AZADO-Cu(NO ３ ) ２ In the case of / GMS, significant acetone production of 55 μmol was confirmed, and the TON was 9.0. From these results, it is clear that the AZADO and co-catalyst (here, Cu ２＋ Cu(NO ３ ) ２ It was found that the oxidation reaction was promoted in a concerted manner when both catalysts were supported on a carrier.

[0076] Cu(NO) was prepared in the same manner as above, except that the reaction temperature was changed to 30°C. ３ ) ２ In addition, AZADO-CuI / GMS was used, which used CuI as a promoter, to produce AZADO-Cu(NO ３ ) ２ The catalytic activity of AZADO-Cu(NO) was compared by applying it to the gas-phase oxidation reaction of 2-propanol at room temperature (30°C) together with AZADO-Cu(NO) / GMS. The time-dependent change in the TON obtained is shown in Figure 8. ３ ) ２ When AZADO-CuI / GMS was used, catalytic acetone production was confirmed even at 30°C. The reaction rate showed a tendency to decrease with the reaction time, and the TON was 7.0 24 hours after the start of the reaction. Catalytic acetone production was also observed with AZADO-CuI / GMS, and the reaction rate remained almost constant. The TON was 3.1 24 hours after the start of the reaction, and the use of Cu(NO ３ ) ２ The activity was lower than that when

[0077] It has been reported that in the reaction in a liquid phase system using AZADO as a catalyst, higher activity can be obtained when copper (I) ions are used than when copper (II) ions are used. On the other hand, in this reaction, a catalyst containing divalent copper (II) ions, Cu(NO), is used, rather than a catalyst containing monovalent copper (I) ions, CuI. ３ ) ２This suggests that the reaction may proceed via a different mechanism in the gas-phase catalytic system than in the liquid-phase system.

[0078] Gas-phase oxidation of 2-propanol in a flow system. In a batch system at 30°C, AZADO-Cu(NO ３ ) ２ When AZADO-Cu(bpy) / GMS was used as a catalyst, a decrease in the reaction rate was observed, which was thought to be due to the rate-limiting effect of the 2-propanol supply. Therefore, in order to examine the catalyst durability, an excess amount of 2-propanol was supplied and the gas-phase oxidation reaction of 2-propanol was carried out in a flow system at 24°C. Specifically, 20 mg of AZADO-Cu(bpy) / GMS was placed in a glass tube with an outer diameter of 1 / 4 inch, and 1.8 mmol / L of 2-propanol was added to the tube. ２ was passed through the reaction system at a flow rate of 50 mL / min, and the reaction was carried out for 24 hours in an incubator maintained at a temperature of 30°C. ３ ) ２ When GMS was used as the catalyst, 20 mg of the catalyst was used, and 2-propanol was added at 1.0 mmol / L. ２ The reaction was carried out at room temperature (24°C) with the catalyst AZADO-Cu(bpy) / GMS being used as the catalyst. ２ was passed through the glass tube at a rate of 20 mL / min, and the lower part of the glass tube was immersed in an oil bath at 30°C to carry out the reaction for 24 hours. At the start of the reaction and after a certain period of time, 1 mL of gas was collected from downstream of the glass tube using a syringe and analyzed by gas chromatography. A flame ionization detector (FID) was used as the detector. The reaction conditions were as follows, and the analysis conditions were the same as above: (Reaction conditions) Catalyst support AZADO-Cu(NO ３ ) ２ / GMS 20mg AZADO-Cu(bpy) / GMS 20mg AZADO-Cu(bpy) / DB 10mg Oxidizing agent AZADO-Cu(NO ３ ) ２ / GMS, AZADO-Cu(bpy) / GMS O ２Flow (20mL / min) AZADO-Cu (bpy) / DB O ２ Flow (50 mL / min) Reaction substrate 2-propanol Reaction temperature AZADO-Cu(NO ３ ) ２ / GMS 24°C (room temperature) AZADO-Cu(bpy) / GMS 30°C (oil bath) AZADO-Cu(bpy) / DB 30°C (incubator) AZADO-Cu(NO ３ ) ２ Figure 9 shows the change in catalyst turnover frequency (TOF) over time when / GMS was used as the catalyst. The TOF showed a value of 21.2 30 minutes after the start of the reaction, then rapidly decreased, and reached 6.4 1 hour after the start of the reaction. The TOF then gradually decreased, reaching 2.0 2.5 hours after the start of the reaction. The TON calculated based on Figure 9 was 29.2, a higher value than the TON (7.0) in the batch system, confirming the improvement in TON.

[0079] [Structural analysis of AZADO-Cu(bpy) / GMS and evaluation of catalytic activity] (Structural analysis of AZADO-Cu(bpy) / GMS) XRD measurement XRD measurement was carried out on the AZADO-Cu(bpy) / GMS prepared above to analyze the structure of the catalyst. ２ The XRD pattern of AZADO-Cu(bpy) / GMS was similar to that of GMS, and the XRD patterns of AZADO, bpy, and Cu(OTf) were similar. ２ It was confirmed that the compound was supported on the GMS in a highly dispersed state.

[0080] Elemental analysis: The prepared AZADO-Cu(bpy) / GMS was subjected to CHN elemental analysis and ICP emission spectroscopy to analyze the contents of C, H, N, and Cu in the catalyst. Here, GMS is composed only of carbon, and the AZADO and Cu(OTf) added during the catalyst preparation were ２ and bpy were all assumed to be supported on GMS.

[0081] From the theoretical and measured values ​​of the content of each element calculated from the amount of each element, it was found that about 84% of the added Cu was supported on GMS. ３ ) ２ It was possible to support more Cu than when using the catalyst (Cu supported amount: 67%). From the comparison of the N content, it was considered that the entire amount of AZADO was supported.

[0082] (Evaluation of catalytic activity) Vapor phase oxidation reaction of 2-propanol in a batch system Figure 10 shows the change in TON over time when the vapor phase oxidation reaction of 2-propanol was carried out in a batch system at 30°C using the AZADO-Cu(bpy) / GMS prepared above as a catalyst. For comparison, the figure also shows the reaction results of various catalysts (Figure 8). When AZADO-Cu(bpy) / GMS was used as a catalyst, the reaction proceeded steadily, and AZADO-Cu(NO ３ ) ２ Although the reaction rate showed a tendency to decrease, the TON was 12.2 24 hours after the start of the reaction. ３ ) ２ The catalytic activity was higher than that of the TON (7.0) when AZADO-Cu(NO ３ ) ２ / GMS uses Cu(NO ３ ) (OH) ３ In contrast to the case of AZADO-Cu(bpy) / GMS, AZADO and Cu(bpy) are highly dispersed on the GMS. Therefore, it is presumed that the proportion of exposed Cu on the surface of AZADO-Cu(bpy) / GMS increases, resulting in improved catalytic activity.

[0083] Gas-phase oxidation reaction of 2-propanol in a flow system For the purpose of examining catalyst durability, AZADO-Cu(bpy) / GMS was used as a catalyst to carry out a gas-phase oxidation reaction of 2-propanol in a flow system at 30°C. The change in TOF over time is shown in Figure 11. The TOF showed 17.6 3 minutes after the start of the reaction, then rapidly decreased, and fell to 2.0 2 hours after the start of the reaction. However, the subsequent decrease in TOF was gradual, and 24 hours after the start of the reaction, the TOF was 0.9. The TON calculated based on Figure 11 was 34.3, a higher value than the TON (12.2) in the batch system, confirming the improvement in TON. Here, the coefficient of determination (R ２ ) was reduced to 0.4491, so TON was calculated using a function that approximated TOF by a power.

[0084] Comparison of catalytic activity between AZADO and TEMPO. It is desirable for a catalyst for gas-phase oxidation to be able to promote the oxidation of sterically hindered substrates. Therefore, TEMPO-Cu(bpy) / GMS, which uses TEMPO as the nitroxyl radical, was prepared using the same procedure as in the "Preparation of AZADO-Cu(bpy) / GMS" above. Then, by applying this catalyst to the gas-phase oxidation of 2-propanol and the gas-phase oxidation of ethanol, together with AZADO-Cu(bpy) / GMS, the activity of each catalyst in both reactions was compared.

[0085] First, Figure 12 shows the TON values ​​24 hours after the start of the batch system gas-phase oxidation of 2-propanol using AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS as catalysts at 30°C. TEMPO-Cu(bpy) / AZADO showed a TON of 1.4 24 hours after the start of the reaction. On the other hand, AZADO-Cu(bpy) / GMS showed a TON of 12.2, approximately nine times more catalytically active than the catalyst using TEMPO as a nitroxyl radical. This indicates that AZADO-Cu(bpy) / GMS is advantageous for the oxidation of sterically hindered alcohols. However, it was previously known that secondary alcohols could not be oxidized using TEMPO as a catalyst in conventional liquid-phase systems. In contrast, it was confirmed that the gas phase oxidation according to the present invention can oxidize secondary alcohols even when TEMPO is used as a catalyst.

[0086] Next, using AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS as catalysts, a gas-phase oxidation reaction of ethanol was carried out in a batch system at 30°C. Specifically, 20 mg of catalyst was weighed into a 100 mL reagent bottle and the bottle was capped with a screw cap designed for dehydrated solvents. Then, oxygen containing 2.5 mmol / L of ethanol was introduced at 50 mL / min for 15 minutes, and the reagent bottle was placed in an incubator maintained at 30°C and the reaction was carried out for 24 hours. At the start of the reaction and after a certain period of time, 1 mL of reaction gas was collected using a gas-tight syringe and analyzed by gas chromatography. The reaction and analysis conditions are shown below.

[0087] (Reaction conditions) Catalyst: AZADO-Cu(bpy) / GMS, TEMPO-Cu(bpy) / GMS, 20 mg each Oxidizing agent: O ２ Reaction substrate: Ethanol Reaction temperature: 30°C (incubator) (Analysis conditions)

[0088]

[0089] The TONs 24 hours after the start of the reaction are shown in Figure 13. 24 hours after the start of the reaction, AZADO-Cu(bpy) / GMS showed a TON of 17, and TEMPO-Cu(bpy) / GMS showed a TON of 6.6, demonstrating that the AZADO-based catalyst exhibited higher activity even when a sterically unhindered alcohol was used as the substrate.

[0090] Control test: In order to confirm that oxygen is the oxidizing agent in the oxidation reaction of 2-propanol described above, a reaction vessel was filled with N ２ The TON at 8 hours after the start of the reaction when the reaction was carried out in a batch system at 30°C for 8 hours using AZADO-Cu(bpy) / GMS as a catalyst was introduced into the reaction system. ２ Under atmospheric conditions, TON was 9.1, whereas under N ２ Under atmospheric conditions, TON was 1.8, and O ２ The TON was reduced to about one-fifth of that in the reaction under atmospheric conditions. ２ It was confirmed that N acts as an oxidizing agent. ２ The reason why TON did not become 0 even under atmospheric conditions is that ２ The replacement of the air inside the reaction vessel by N ２ It is thought that air was mixed in when the O was introduced, or that air was mixed in due to a decrease in the internal pressure of the reaction vessel caused by the collection of the gas sample. ２ Even in the absence of AZADO or AZADO ＋ It is thought that an oxidation reaction occurs due to the oxidation of N2O3, and the TON value is thought to be a maximum of 1. In this test, the contribution of both of these factors is ２ It is presumed that TON did not become 0 even under atmospheric conditions.

[0091] In addition, synthetic air containing 1.8 mmol / L of 2-propanol was introduced into the reaction vessel, and the reaction was carried out in a batch system at 30°C for 24 hours using AZADO-Cu(bpy) / GMS as a catalyst. The change in TON over time is shown in Figure 15. As a result, ２Although the reaction rate was slower than when synthetic air was used, the reaction proceeded steadily. ２ The value was approximately 65% ​​of that when using synthetic air (TON 12.2). ２ The proportion of pure O ２ Although it is about one-fifth of the pure O ２ It was confirmed that the activity was 65% of that when the catalyst was introduced, and the oxidation reaction was sufficiently promoted even in air.

[0092] [Structural analysis and catalytic activity evaluation of AZADO-Cu(bpy)-based catalysts using various carbon materials and oxides as supports] (Structural analysis of AZADO-Cu(bpy)-based catalysts by XRD measurement) The structure of catalysts prepared by supporting AZADO and Cu(bpy) on various carbon materials and oxides was analyzed by XRD measurement. As a result, the XRD patterns obtained for all catalysts were equivalent to those of the carbon materials used, confirming that AZADO and Cu(bpy) were supported in a highly dispersed state on each support.

[0093] Furthermore, for the catalysts prepared using various oxide supports, the XRD patterns obtained for all catalysts were equivalent to those of the oxide supports used, confirming that AZADO and Cu(bpy) were highly dispersed on each support.

[0094] (Evaluation of Catalytic Activity) - Gas-Phase Oxidation of 2-Propanol in a Batch System Figure 16 shows the time-dependent changes in TON obtained for catalysts using various carbon materials as supports when the gas-phase oxidation of 2-propanol was carried out in a batch system using catalysts in which AZADO and Cu(bpy) were supported on various carbon materials and oxides. The TONs obtained using AZADO-Cu(bpy) / GMS, AZADO-Cu(bpy) / YP-50F, AZADO-Cu(bpy) / KB, and AZADO-Cu(bpy) / VC catalysts exhibited similar behavior for the first 2 hours after the start of the reaction, and then decreased with the passage of reaction time. Thereafter, the reaction rates of the catalysts using YP-50F and KB as supports decreased by approximately the same magnitude, and the TONs at 24 hours after the start of the reaction were 16 and 15, respectively. The catalyst using GMS as a carrier showed a greater decrease in reaction rate than the catalysts using YP-50F and KB as carriers, with a TON of 12 at 24 hours after the start of the reaction. On the other hand, the catalyst using VC as a carrier showed almost no decrease in reaction rate, and the TON at 24 hours after the start of the reaction was a high value of 28. The initial reaction rate with AZADO-Cu(bpy) / DB was the highest, and, as with the VC carrier, almost no decrease in reaction rate was observed. The TON at 24 hours after the start of the reaction was the highest, at 34. With AZADO-Cu(bpy) / CMS, the reaction rate up to 4 hours after the start of the reaction was less than half that of the catalysts using GMS, YP-50F, KB, VC, and DB as carriers, but the reaction rate did not decrease after 4 hours and remained nearly constant, resulting in a TON of 10 at 24 hours after the start of the reaction. Although the reaction proceeded with AZADO-Cu(bpy) / ZTC, the TON 24 hours after the start of the reaction was as low as 0.6.

[0095] Next, the time-dependent changes in TON obtained for catalysts using various oxides as supports are shown in Figure 17. Although the reaction proceeded with AZADO-Cu(bpy) / MgO, the reaction rate was slow, and the TON was 1 24 hours after the start of the reaction. ２Although the initial reaction rate was the lowest in the case of AZADO-Cu(bpy) / silica gel and AZADO-Cu(bpy) / fumed silica catalysts, the reaction continued to proceed slowly, with a TON of 2 24 hours after the start of the reaction. In the case of AZADO-Cu(bpy) / silica gel and AZADO-Cu(bpy) / fumed silica catalysts, the reaction continued to proceed slowly, with a TON of 7 and 6 24 hours after the start of the reaction, respectively. ２ O ３ The reaction proceeded rapidly immediately after the start of the reaction. After that, the reaction rate decreased exponentially, but the TON reached a maximum value of 20 24 hours after the start of the reaction. The TON in the case of AZADO-Cu(bpy) / zeolite was also ２ O ３ The TON 24 hours after the start of the reaction was a relatively high value of 14. ２ In the case of Al, the initial reaction rate was lower than when zeolite was used as a carrier, but there was almost no decrease in the reaction rate, and the TON 24 hours after the start of the reaction was 17, which was higher than when zeolite was used as a carrier. ２ O ３ The value was the second highest when Al was used as the support. ２ O ３ The catalyst using Al as a support showed high catalytic activity, possibly due to the promotion of the oxidation reaction by the generation of oxoammonium ions. As mentioned above, nitroxyl radicals are oxidized to generate oxoammonium ions. ２ O ３ is known to have solid acidity. ２ O ３ It is presumed that the disproportionation reaction of AZADO occurs due to the solid acidity of CeO, and the generated oxoammonium ions promote the oxidation reaction. ２ When the support was used, it is possible that the oxidation reaction was promoted by the redox reaction of Ce.

[0096] - Study of the support effect In the above study, a gas-phase oxidation reaction of 2-propanol was carried out using catalysts in which AZADO and Cu(bpy) were supported on various carbon materials, and it was shown that the catalytic activity varies depending on the carbon material used as the support. Therefore, the TON was plotted against the specific surface area, total pore volume, edge amount, and spin density of each carbon material obtained 24 hours after the start of the reaction using catalysts supported on various carbon materials, and the correlation with TON was examined. The obtained plot is shown in Figure 18. When TON was plotted against the specific surface area, the obtained R ２ The value was 0.8585, indicating a strong negative correlation between them (Fig. 18(a)). From this, it was inferred that AZADO and Cu(bpy) can exist in close proximity on a carbon support with a low specific surface area, which efficiently promotes the oxidation reaction and results in a large TON. This contradicts the conventional wisdom that, in general, the larger the specific surface area of ​​a catalyst support, the higher the catalytic activity. Furthermore, when TON is plotted against the total pore volume, R ２ The value was 0.2108, and it was found that there was almost no correlation between these values ​​(FIG. 18(b)). When TON was plotted against the edge amount, R ２ The value was 0.5779, which indicates a weak negative correlation, but it was found to be smaller than the correlation between the specific surface area and TON (FIG. 18(c)). In addition, when TON was plotted against the spin density, R ２ The value was 0.6612, suggesting a relatively strong negative correlation (FIG. 18(d)).

[0097] The above study demonstrated a strong negative correlation between the activity of catalysts using carbon materials as supports and the specific surface area of ​​each carbon material. Therefore, the TON values ​​obtained 24 hours after the start of the reaction using catalysts with various oxide supports were organized by the specific surface area of ​​each oxide and compared with those obtained using carbon supports. Figure 19 shows a plot of the TON 24 hours after the start of the reaction versus the specific surface area of ​​each oxide support. Figure 19 also shows plots for various carbon supports. The plots demonstrated that all oxide supports exhibited lower activity than carbon supports with equivalent specific surface areas. These results demonstrate that a carbon support is particularly useful in this catalyst system using a solid catalyst supporting AZADO and Cu(bpy). Among these, the TON of 36 was obtained when Denka Black was used as the support, achieving the highest catalytic activity. This is because Denka Black has a specific surface area of ​​68 m². ２ / g, which is presumably because AZADO and Cu(bpy) could exist in close proximity to each other.

[0098] The results shown above demonstrate that, according to the present invention, organic compounds can be oxidized in the gas phase using nitroxyl radicals as a catalyst.

[0099] This application is based on Japanese Patent Application No. 2022-136100, filed on August 29, 2022, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. The present invention comprises a support having a compound having the following oxidation-reduction mechanism and a co-catalyst containing a transition metal, The carrier is 50 to 3000 m ２ A catalyst support comprising one or more porous carbon materials selected from the group consisting of graphene meso sponge, carbon meso sponge, zeolite template carbon, Ketjen Black, Vulcan, and Denka Black, having a BET specific surface area of ​​100 nm to 100 nm / g: 【Chemistry 1】 In the formula, X － is a counter anion, and the dashed lines represent the bond positions to other atoms.

2. The standard redox potential (25° C.) between the nitroxyl radical form and the oxoammonium form is +100 mV to +1000 mV [Ag / Ag ＋ 2. The catalyst support according to claim 1, wherein

3. 2. The catalyst support of claim 1, wherein the nitroxyl radical form of the compound is represented by the following chemical formula 1: 【Chemistry 2】 In the formula, R １ ~R ４ , Y １ and Y ２ are each independently a hydrogen atom or an optionally substituted monovalent organic group, １ and Y ２ may be bonded to each other to form an optionally substituted nitrogen-containing monocyclo ring containing a 5- or 6-membered ring, and R １ and R ３ may be bonded to each other to form an optionally substituted nitrogen-containing bicyclo ring containing a 5- or 6-membered ring, or two rings constituting the nitrogen-containing bicyclo ring may be further bridged to form an optionally substituted nitrogen-containing tricyclo ring containing a 5- or 6-membered ring.

4. The catalyst support of claim 3, wherein the nitroxyl radical form of the compound is represented by the following chemical formula 2: 【Chemistry 3】 In the formula, R １ ~R ４ are each independently a hydrogen atom or an optionally substituted monovalent organic group, Z is an optionally substituted nitrogen-containing monocyclo ring containing a 5- or 6-membered ring, in which case R １ and R ３ may be bonded to each other to form an optionally substituted nitrogen-containing bicyclo ring containing a 5- or 6-membered ring, or two rings constituting the nitrogen-containing bicyclo ring may be further bridged to form an optionally substituted nitrogen-containing tricyclo ring containing a 5- or 6-membered ring.

5. When the compound does not contain the monocyclo, bicyclo or tricyclo ring or contains the nitrogen-containing monocyclo ring, R １ ~R ４ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, When the compound contains the nitrogen-containing bicyclo ring or the nitrogen-containing tricyclo ring, R ２ and R ４ and each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

6. 3. The catalyst support according to claim 1 or 2, wherein the nitroxyl radical form of the compound is one or more selected from the following group: 【Chemistry 4-1】 【Chemistry 4-2】

7. 7. The catalyst support of claim 6, wherein the nitroxyl radical form of the compound is 2-azaadamantane-N-oxyl (AZADO).

8. 3. The catalyst support according to claim 1, wherein the transition metal comprises one or more selected from the group consisting of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn and Cu.

9. The catalyst support of claim 8 , wherein the transition metal comprises Cu.

10. 3. The catalyst support according to claim 1, wherein a molar ratio of the supported amount of said compound to the supported amount of said transition metal is 1:2 to 4:1 (compound:transition metal).

11. 3. The catalyst support according to claim 1, wherein the coverage of the surface area of ​​the support by the compound and the co-catalyst is 10 to 300%.

12. The following redox mechanism: 【Chemistry 5】 In the formula, X － is a counter anion, and the dashed lines represent the bond positions to other atoms. and a co-catalyst containing a transition metal, the co-catalyst being supported on a carrier.

13. In the gas phase in the presence of molecular oxygen, the following oxidation-reduction mechanism occurs: 【Chemistry 6】 In the formula, X － is a counter anion, and the dashed lines represent the bond positions to other atoms. and a co-catalyst containing a transition metal, supported on a carrier.

14. 14. The gas phase oxidation process of claim 13, wherein the organic compound is a volatile organic compound.

15. 15. The gas phase oxidation method according to claim 13 or 14, wherein the organic compound is a primary alcohol or a secondary alcohol.

16. The following redox mechanism: 【Chemistry 7】 In the formula, X － is a counter anion, and the dashed lines represent the bond positions to other atoms. and a co-catalyst containing a transition metal are supported on a carrier, and the catalyst-supported body is supported or coated on a base substrate, and the catalyst-containing substrate is used in masks, medical textile products, air conditioners, air purifiers, freezers, temperature regulators, dehumidifiers, humidifiers, or suction vacuum cleaner filters.

17. 17. The catalyst-containing substrate according to claim 16, wherein the base substrate is a woven fabric, a nonwoven fabric, a filter or a urethane foam.

18. A spray container and a redox mechanism contained in the spray container, the redox mechanism being as follows: 【Chemistry 8】 In the formula, X － is a counter anion, and the dashed lines represent the bond positions to other atoms. and a solution in which a catalyst support in which a compound having the formula (I) and a co-catalyst containing a transition metal are dispersed, the catalyst support being formed by supporting the compound on a support.

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