Catalyst support, catalyst for gas-phase oxidation of organic compound using catalyst support, and method for gas-phase oxidation

Abstract

[Problem] To provide a means by which an organic compound can be oxidized in the gas phase using a nitroxyl radical as a catalyst. [Solution] A compound having a redox mechanism (in the formula, X-is a counter anion, and the dashed line represents a bonding position with another atom) is supported on a carrier together with a promoter containing a transition metal to form a catalyst support. # imgabs0 #

Description

Technical Field

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

[0002] Nitroxyl radical is a stable organic free radical molecule, and is widely used as an oxidation catalyst in the field of organic synthesis. In particular, organic nitroxyl radicals exhibit reactivity in both oxidation and reduction directions. As shown in the following reaction formula, a one-electron reduction reaction produces hydroxylamine, and a one-electron oxidation reaction produces oxoammonium ions.

[0003] [Chemical formula 1]

[0004]

[0005] The oxoammonium ions generated by the oxidation of nitroxyl radicals have strong oxidizing ability and can obtain hydroxylamine after two-electron oxidation of the substrate. In the oxidation reaction in which the oxoammonium ions act as oxidizing active substances, the oxoammonium ions can be regenerated by adding a reactant that promotes the reoxidation of the hydroxylamine to complete the cycle and act as a catalyst.

[0006] As such an oxidation catalyst, 2,2,6,6-tetramethylpiperidinyl 1-oxyl (TEMPO) is known in the past. In addition, 2-azaadamantane-N-oxyl (AZADO) is proposed as a catalyst for improving the large steric hindrance of TEMPO (see International Publication No. 2006 / 001387). The AZADO can achieve highly efficient oxidation of various alcohols with large steric hindrance to corresponding carbonyl compounds.

[0007] On the other hand, in recent years, from the viewpoint of reducing environmental load, oxidation reactions using oxygen in the air as an oxidant have received great attention. For example, Iwabuchi reported that the oxidation of various alcohols can be efficiently promoted in a reaction system such as AZADO / NaNO2 / O2 using AZADO and 5-fluoro-AZADO (see M. Shibuya, Y. Osada, Y. Sasano, M. Tomizawa, Y. Iwabuchi, J. Am. Chem. Soc. 2011, 133, 6497-6500.).

[0008] It should be noted that the technologies described in the International Publication No. 2006 / 001387, M. Shibuya, Y. Osada, Y. Sasano, M. Tomizawa, Y. Iwabuchi, J. Am. Chem. Soc. 2011, 133, 6497-6500, are all for oxidizing alcohols to corresponding aldehydes or ketones in a liquid phase system, and there has been no report to date on technologies for oxidizing alcohols in the gas phase using nitroxyl radicals such as TEMPO and AZADO as catalysts. Summary of the invention

[0009] Technical problem solved by the invention

[0010] In the case of a liquid phase reaction as described in the literature, the target product and the catalyst must be separated from the solvent after the reaction is completed, and the target product must be further purified, which is problematic in terms of time and cost.

[0011] Therefore, an object of the present invention is to provide a technology capable of oxidizing an organic compound in a gas phase by using a nitroxyl radical as a catalyst.

[0012] Technical means of solving problems

[0013] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by a catalyst support in which a compound having a redox mechanism represented by the above reaction formula is supported on a support together with a co-catalyst, thereby completing the present invention.

[0014] That is, one embodiment of the present invention is a catalyst support obtained by supporting a compound having the following redox mechanism and a co-catalyst containing a transition metal on a support,

[0015] [Chemical formula 2]

[0016]

[0017] Where, X - For counter anions, dashed lines indicate bonding sites to other atoms.

[0018] Effects of the Invention

[0019] According to the present invention, it is possible to oxidize an organic compound in a gas phase by using a nitroxyl radical as a catalyst. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] [ Figure 1 ] Figure 1The standard redox potential (E) between the nitroxyl radical form and the oxoammonium form was measured for four compounds: (a) TEMPO, (b) AZADO, (c) 1-methyl AZADO, and (d) 1,3-dimethyl AZADO by using cyclic voltammetry. 0 @25℃) and obtained cyclic voltammogram.

[0021] [ Figure 2 ] Figure 2 This is an XRD pattern showing the results of XRD measurement of AZADO / GMS prepared in Examples together with the measurement results of AZADO and GMS.

[0022] [ Figure 3 ] Figure 3 This is an ESR spectrum showing the results of ESR measurement of AZADO / GMS prepared in Examples.

[0023] [ Figure 4 ] Figure 4 This is a graph showing the results of a gas-phase oxidation reaction of 2-propanol carried out at 80°C in a batch system using AZADO / GMS prepared in the example as a catalyst (acetone production 24 hours after the start of the reaction), together with the results of a case where only GMS was used as a catalyst and a case where no catalyst was used (blank).

[0024] [ Figure 5 ] Figure 5 It is an XRD pattern showing the results of XRD measurement of AZADO-Cu(NO3)2 / GMS, AZADO-CuI / GMS and AZADO-Fe(NO3)3 / GMS prepared in Examples.

[0025] [ Figure 6 ] Figure 6 This is an XRD pattern showing the results of XRD measurement of AZADO-Cu(NO3)2 / GMS prepared in the example together with the measurement results of Cu(NO3)2·3H2O and Cu2(NO3)(OH)3.

[0026] [ Figure 7 ] Figure 7 This is a graph showing the results of the gas-phase oxidation reaction of 2-propanol in a batch system using AZADO-Cu(NO3)2 / GMS, Cu(NO3)2 / GMS and AZADO / GMS prepared in the example as catalysts (acetone production 24 hours after the start of the reaction at 80°C) together with the results when only GMS was used as a catalyst.

[0027] [ Figure 8 ] Figure 8 This is a graph showing the results of using AZADO-Cu(NO3)2 / GMS and AZ ADO-CuI / GMS prepared in the example as catalysts and applying them to the gas-phase oxidation reaction of 2-propanol at room temperature (30°C) in a batch system, and the change in TON (Turnover Number) as an indicator of catalytic activity over time.

[0028] [ Fig. 9 ] Fig. 9 This is a graph showing the results of the gas-phase oxidation reaction of 2-propanol carried out at room temperature (24°C) in a flow system (O2 containing 1.0 mmol / L 2-propanol was circulated at a rate of 20 mL / min) using AZADO-Cu(NO3)2 / GMS prepared in the example as a catalyst, and the change in T OF (Turnover Frequency) as an indicator of catalytic activity over time.

[0029] [ Fig.10 ] Fig.10 This is a graph showing the results of the gas-phase oxidation reaction (30°C) of 2-propanol in a batch system using AZADO-Cu(bpy) / GMS prepared in the example as a catalyst (change in TON over time) and the results when AZADO-Cu(NO3)2 / GMS, AZADO-CuI / GMS or AZADO / GMS was used as a catalyst.

[0030] [ Fig.11 ] Fig.11 This is a graph showing the change in TOF over time, showing the result of a gas-phase oxidation reaction of 2-propanol at 30°C in a flow system (O2 containing 1.8 mmol / L of 2-propanol was circulated at a rate of 50 mL / min) using AZADO-Cu(bpy) / GMS prepared in the example as a catalyst.

[0031] [ Fig.12 ] Fig.12 This is a chart comparing the TON 24 hours after the start of the reaction when the gas-phase oxidation reaction of 2-propanol was carried out at 30°C in a batch system using AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS prepared in the example as catalysts.

[0032] [ Fig.13 ] Fig.13This is a chart comparing the TON 24 hours after the start of the reaction when the AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS prepared in the example were used as catalysts to carry out the gas-phase oxidation reaction of ethanol at 30°C in a batch system.

[0033] [ Fig.14 ] Fig.14 This is a chart comparing the TON 8 hours after the start of the reaction when N2 containing 1.8 mmol / L 2-propanol was introduced into the reaction container, AZADO-Cu(bpy) / GMS was used as a catalyst, and the reaction was carried out at 30°C for 8 hours in a batch system, and the reaction was compared with the situation under O2 atmosphere.

[0034] [ Fig.15 ] Fig.15 This is a graph comparing the change in TON over time when synthetic air containing 1.8 mmol / L of 2-propanol was introduced into a reaction container, AZADO-Cu(bpy) / GMS was used as a catalyst, and the reaction was carried out at 30°C for 24 hours in a batch system, with the situation under O2 atmosphere.

[0035] [ Fig.16 ] Fig.16 This is a graph showing the change over time of 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(b py) were supported on various carbon materials and oxides.

[0036] [ Fig.17 ] Fig.17 This is a graph showing the change over time of 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(b py) were supported on various carbon materials and oxides.

[0037] [ Fig.18 ] Fig.18 The scatter plots are plotted to show TON for the specific surface area, total pore volume, edge volume, and spin density of each carbon material 24 hours after the start of the reaction, which are obtained using catalysts supported on various carbon materials.

[0038] [ Fig.19 ] Fig.19 The TON 24 hours after the start of the reaction obtained by using catalysts with various oxides as carriers is sorted out by the specific surface area of ​​each oxide. In order to compare with the case where a carbon carrier is used, the TON 24 hours after the start of the reaction relative to the specific surface area of ​​each oxide carrier is plotted to obtain a scatter plot. It should be noted that Fig.19 The cases where various carbon supports were used Figure 1 And stated. DETAILED DESCRIPTION

[0039] Hereinafter, specific embodiments of the present invention will be described.

[0040] <<Catalyst Support>>

[0041] One embodiment of the present invention is a catalyst support, which is obtained by loading a compound having the above-mentioned redox mechanism (hereinafter also referred to as "the compound of the present embodiment") and a co-catalyst containing a transition metal (hereinafter also referred to as "the co-catalyst of the present embodiment") onto a carrier (hereinafter also referred to as "the carrier of the present embodiment").

[0042] <Compounds of the present embodiment>

[0043] The compound of this embodiment has the redox mechanism described above, and there is no limitation on its specific structure. In addition, the compound of this embodiment, when loaded on a carrier, can be in the hydroxylamine form, nitroxyl radical form, or oxoammonium form in the redox mechanism described above. Among them, the hydroxylamine form or the nitroxyl radical form is preferred, and the nitroxyl radical form is particularly preferred.

[0044] In addition, from the viewpoint of exhibiting excellent catalytic activity when used as an oxidation catalyst described below, the standard redox 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 + ], more preferably +130mV to +600mV [Ag / Ag + ]. It should be noted that the standard redox potential was measured by cyclic voltammetry (CV) at a temperature of 25°C. At this time, a glassy carbon electrode (inner diameter 3 mm) was used as the working electrode and a reference electrode (Ag / Ag + ) and a counter electrode (platinum wire) in a three-pole mode, with a potential scan rate of 50 mV / s. It should be noted that the hydroxylamine form of the compound of this mode is generally unstable and is rapidly oxidized to a nitroxyl radical form. Therefore, the value of the standard redox potential measured by the method described is a value between the nitroxyl radical form and the oxoammonium form.

[0045] Here, among the compounds of the present embodiment, for four compounds, namely (a) TEMPO, (b) AZADO, (c) 1-methyl AZADO and (d) 1,3-dimethyl AZADO, the standard redox potential (E) between the nitroxyl radical form and the oxoammonium form was measured by using the cyclic voltammetry method. 0 The cyclic voltammogram obtained by Figure 1 As shown. Figure 1 As shown in the figure, the E 0 The values ​​are (d) 136mV < (c) 186mV < (b) 236mV < (a) 294mV. It should be noted that for Figure 1 As can be seen from the cyclic voltammogram shown, even when the measurement is repeated for more than 100 cycles, the stability can be maintained, and thus the compound of the present embodiment has very high durability as an oxidizing agent.

[0046] From the viewpoint of catalytic activity, the compound of the present embodiment is preferably in the form of a nitroxyl radical as represented by the following compound formula 1.

[0047] [Chemical formula 3]

[0048] [Compound Formula 1]

[0049]

[0050] In compound formula 1, R1 to R4, Y1 and Y2 are each independent and are a hydrogen atom or an optionally substituted monovalent organic group. Here, the monovalent organic group is not particularly limited, and for example, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, etc. may be cited. It should be noted that R1 to R4, Y1 and Y2 may be the same or different.

[0051] The alkyl, alkenyl and alkynyl groups as monovalent organic groups may be any of linear, branched or cyclic, preferably linear. The number of carbon atoms in the alkyl group is not particularly limited, preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and further preferably 1 or more and 4 or less. The number of carbon atoms in the alkenyl and alkynyl groups is not particularly limited, preferably 2 or more and 20 or less, more preferably 2 or more and 10 or less, and further preferably 2 or more and 4 or less.

[0052] The aryl group as a monovalent organic group is a group derived from a hydrocarbon ring having aromaticity as a part or as a whole. When the aryl group contains more than two hydrocarbon rings having aromaticity as a part or as a whole, these rings can be bonded or condensed to each other with a single bond. In addition, when the aryl group contains more than two hydrocarbon rings having aromaticity as a part or as a whole, one atom can serve as a ring-forming atom of any two of these rings to form a spiro ring. The number of carbon atoms of the aryl group is not particularly limited, preferably more than 6 and less than 30. The number of carbon atoms of the aryl group is more preferably more than 6 and less than 12, and more preferably 6. In particular, the aryl group is preferably a monovalent group derived from an aromatic hydrocarbon ring having more than 6 ring-forming atoms.

[0053] The heteroaryl group as a monovalent organic group is a group derived from a heterocyclic ring having aromaticity as a part or as a whole. When the heteroaryl group contains more than two heterocyclic rings having aromaticity as a part or as a whole, a part or all of these rings can be bonded to each other with a single bond. When the heteroaryl group contains more than two heterocyclic rings or other rings having aromaticity as a part or as a whole, these rings can be fused to each other. In addition, when the heteroaryl group contains more than two heterocyclic rings or other rings having aromaticity as a part or as a whole, one atom can also serve as a ring-forming atom of these rings. The heteroatom possessed by the heteroaryl group is not particularly limited, for example, as a ring-forming atom, more than one heteroatom (for example, nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom (S), silicon atom (Si), selenium atom (Se), germanium atom (Ge)) etc. can be cited. The number of carbon atoms of the heteroaryl group is preferably more than 3 and less than 30. In addition, the number of ring-forming atoms of the heteroaryl group is not particularly limited, preferably more than 5 and less than 30. In addition, the number of ring atoms of the heteroaryl group is more preferably 5 or more and 14 or less, and further preferably 5 or more and 13 or less. The number of heteroatoms of the heteroaryl group is not particularly limited, but is preferably 1 or more and 3 or less. In addition, the number of heteroatoms of the heteroaryl group is more preferably 1 or more and 2 or less, and further preferably 1. In particular, the heteroaryl group is preferably a monovalent group derived from an aromatic heterocycle having 5 or more ring atoms.

[0054] The alkyl, alkenyl, alkynyl, aryl and heteroaryl groups as monovalent organic groups can be substituted groups. There is no particular limitation on the substituent, and for example, alkyl, alkoxy, alkenyl, alkynyl, halogen atom, hydroxyl, carboxyl, cyano, amino, carbamoyl and the like can be cited. Among them, as a substituent, preferably an alkyl or a halogen atom, more preferably a methyl, ethyl or fluorine atom. And, as a substituent, more preferably a methyl or fluorine atom. It should be noted that the substituent will not replace the same group. For example, the substituent of the substituted alkyl does not contain an alkyl.

[0055] In addition, in compound formula 1, from the viewpoint of excellent catalytic activity, it is preferred that Y1 and Y2 are bonded to each other to form a nitrogen-containing monocyclic ring containing a 5-membered ring or a 6-membered ring, and R1 and R3 are bonded to each other to form a nitrogen-containing bicyclic ring containing a 5-membered ring or a 6-membered ring, or the two rings constituting the nitrogen-containing bicyclic ring are further cross-linked to form a nitrogen-containing tricyclic ring containing a 5-membered ring or a 6-membered ring. That is, in a preferred embodiment of the present embodiment, the nitroxyl radical form of the compound of the present embodiment is shown in the following compound formula 2.

[0056] [Chemical formula 4]

[0057] [Compound Formula 2]

[0058]

[0059] In compound formula 2, R1 to R4 are independently a hydrogen atom or an optionally substituted monovalent organic group, and Z is an optionally substituted nitrogen-containing monocyclic ring containing a 5-membered ring or a 6-membered ring. In this case, R1 and R3 are further optionally bonded to each other to form an optionally substituted nitrogen-containing bicyclic ring containing a 5-membered ring or a 6-membered ring, or the two rings constituting the nitrogen-containing bicyclic ring are further cross-linked to form an optionally substituted nitrogen-containing tricyclic ring containing a 5-membered ring or a 6-membered ring.

[0060] As the nitrogen-containing monocyclic ring of Z, for example, aliphatic heterocyclic rings such as tetrahydropyrrole ring, piperidine ring, morpholine ring, pyrroline ring, aromatic heterocyclic rings such as pyrrole ring, imidazole ring, etc. can be cited. In addition, as a nitrogen-containing bicyclic ring formed by further bonding R1 and R3 to each other, for example, 9-azabicyclo [3.3.1] nonane ring, 9-aza-3-oxabicyclo [3.3.1] nonane ring can be cited. And, as a nitrogen-containing tricyclic ring formed by further cross-linking the two rings constituting the nitrogen-containing bicyclic ring, for example, 2-azaadamantane ring, 2,6-diazaadamantane ring, 6-aza-2-oxadamantane ring, 9-aza-6-noradamantane ring can be cited. Among them, from the viewpoint of excellent catalytic activity, the compound of this mode preferably has a nitrogen-containing monocyclic ring, a nitrogen-containing bicyclic ring or a nitrogen-containing tricyclic ring, more preferably has a nitrogen-containing monocyclic ring or a nitrogen-containing tricyclic ring, and particularly preferably has a nitrogen-containing tricyclic ring. The compound of this embodiment preferably has a nitrogen-containing monocyclic aliphatic heterocyclic ring or a nitrogen-containing tricyclic 2-azaadamantane ring or 9-aza-6-noradamantane ring, and more preferably has a nitrogen-containing monocyclic piperidine ring or a nitrogen-containing tricyclic 2-azaadamantane ring.

[0061] The nitrogen-containing monocyclic ring formed in the compound formula 2 or the nitrogen-containing bicyclic ring or nitrogen-containing tricyclic ring formed in the compound formula 2 is an optionally substituted ring structure. There is no particular limitation on the substituents that can replace these ring structures, and for example, alkyl, alkoxy, alkenyl, alkynyl, halogen atoms, hydroxyl, carboxyl, carbonyl, cyano, amino, carbamoyl, tosyl, (halogenated) acylamino, phosphoric acid, etc. can be cited. Among them, as a substituent, a methyl, ethyl, methoxy, ethoxy, fluorine atom, hydroxyl, carboxyl or tosyl group is more preferred.

[0062] Here, when the compound of the present embodiment does not contain the ring structure or contains a nitrogen-containing monocyclic ring, R1 to R4 are each independently, preferably a hydrogen atom or an optionally substituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group, further 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. In addition, from the viewpoint of catalytic activity, when the compound of the present embodiment contains the nitrogen-containing bicyclic ring or nitrogen-containing tricyclic ring, R2 and R4 are each independently, preferably a hydrogen atom or an optionally substituted alkyl group, more preferably a hydrogen atom or an unsubstituted alkyl group, further 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.

[0063] When an example of a compound of the present embodiment is given, it is shown below (expressed in the form of nitroxyl radical). It should be noted that for some compounds, the value of the standard redox potential (25° C.) between the nitroxyl radical form and the oxoammonium form is also recorded. In view of the mechanism by which the catalyst support of the present embodiment exhibits excellent catalytic activity, it can be said that the compounds shown below all exhibit high antimicrobial activity.

[0064] [Chemical formula 5-1]

[0065]

[0066] [Chemical formula 5-2]

[0067]

[0068] [Chemical formula 5-3]

[0069]

[0070] Given the E 0 When heteroatoms are introduced into structures such as TEMPO, ABNO, and AZADO constituting the skeleton of the compound, the redox characteristics of the compound of this embodiment shift to the high potential side. It is believed that the oxidation ability of the potential corresponding to each oxoammonium form is improved.

[0071] Among the above compounds, preferred from the viewpoint of catalytic activity are TEMPO, 4-hydroxyTEMPO, 4-methoxyTEMPO, 4-acetylaminoTEMPO, 4-oxoTEMPO, 4-carboxyTEMPO, 4-aminoTEMPO, 4-phosphonoTEMPO, 4-(2-bromoacetamide)TEMPO, AZADO, 1-methylAZADO, 1,3-dimethylAZADO, 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, AZADO, di-AZADO or Nor-AZADO, more preferably AZADO, 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 Preferably, the AZADO is 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, or 5,7-dimethoxy AZADO, and AZADO (2-azaadamantane-N-oxyl) is particularly preferred.

[0072] <Promoter of the present embodiment>

[0073] In the catalyst carrier of this mode, the compound is supported on a carrier together with a co-catalyst. Here, the co-catalyst of this mode includes a transition metal. It should be noted that the co-catalyst can be in the form of a transition metal monomer or in the form of a transition metal compound (e.g., salt, complex). The transition metal that can be included in the co-catalyst of this mode is a metal element classified as a metal element from the 3rd group element to the 12th group element of the periodic table, and is not particularly limited. Among them, from the viewpoint of excellent catalytic activity, the transition metal preferably includes one or more of Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn and Cu, and more preferably includes its ion (salt). In addition, the transition metal further preferably includes Cu, particularly preferably includes Cu ions (salts), and most preferably includes divalent Cu ions (Cu (II) ions). It should be noted that it has been reported in the past that in the reaction in the liquid phase system of AZADO for the catalyst, the case where Cu (I) ions are used is compared with the case where Cu (II) ions are used to obtain higher activity. On the other hand, it was confirmed that in the reaction using the catalyst support of the present embodiment, the catalyst containing divalent Cu(II) ions exhibited higher activity than the catalyst containing monovalent Cu(I) ions.

[0074] In the case where the co-catalyst comprises the ion (salt) of transition metal, the counter anion of the ion is not particularly limited. As the salt comprising transition metal of co-catalyst, for example, sulfate, sulfite, hyposulfite, persulfate, thiosulfate, carbonate, phosphate, pyrophosphoric acid, hydrochloride, nitrate, nitrite, halide (for example, fluoride, chloride, bromide, iodide), triflate etc. can be enumerated. But, preferably comprise transition metal in the mode of divalent ion as mentioned above.

[0075] There is no particular limitation on the amount of the compound and the transition metal supported in the catalyst support of the present embodiment. From the viewpoint of excellent catalytic activity, the molar ratio of the supported amounts of these components is preferably 1:2 to 4:1 (compound: transition metal), and more preferably 2:3 to 3:2. In addition, as described in detail below, the coverage of the compound and the co-catalyst in the surface area of ​​the support is preferably 10 to 300% from the viewpoint of catalytic activity. It should be noted that for the value of the coverage, the size of the compound and the co-catalyst (metal, ligand) of the present embodiment can be approximated to a circle or a rectangle, the coverage of the support surface based on each component is calculated, and all of them are added together to obtain the value. For example, when AZADO-Cu(bpy) is taken as an example, for AZADO, it can be approximated to the same size as cyclohexane (one side is square), for Cu in Cu(bpy), it can be approximated by the radius The circle of bpy is approximately Here, when the coverage value exceeds 100%, it is considered that after a complete coating layer based on the component is formed on the surface of the carrier, the component is further laminated on the complete coating layer. The coverage value can be controlled by adjusting the amount of each component when manufacturing the catalyst support.

[0076] The catalyst carrier of this mode needs to be loaded with the compound and transition metal on the carrier, and other components can be further loaded as needed. As other components, for example, ligands can be cited. Catalytic activity can be further improved by further loading ligands. At this time, transition metals and ligands can form complexes. It is possible to suitably use the ligands known in the past, preferably compounds containing nitrogen-containing 6-membered rings. Wherein, as ligands, more preferably compounds containing pyridine rings, more preferably bipyridine compounds, terpyridine compounds or phenanthroline compounds. As specific examples of these compounds, 2,2'-bipyridine (bpy), 2,6-bis(2-pyridyl)pyridine, 1,10-phenanthroline, 4,7-biphenyl-1,10-phenanthroline, 1,7-phenanthroline, bathocuproin, bathocuproin sulfonic acid, etc., are particularly preferably 2,2'-bipyridine (bpy). When a ligand is used, the loading amount is not particularly limited. 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.

[0077] <Carrier of this method>

[0078] There is no particular limitation on the specific composition of the carrier of this embodiment, and it is possible to refer to the previously known contents as appropriate. As a carrier, for example, metal oxides or carbon materials can be cited, and carbon materials are more preferably mentioned. As metal oxides that can be used as carriers, for example, silicon dioxide (silica gel, fumed silica, etc.), aluminum oxide (α aluminum oxide, θ aluminum oxide, γ aluminum oxide, δ aluminum oxide, β aluminum oxide, etc.), titanium dioxide, ceria, silicon dioxide alumina, zirconium oxide, magnesium oxide, zeolite, etc. can be cited. When a metal oxide is used as a carrier, the metal oxide is preferably aluminum oxide, titanium dioxide or ceria, and more preferably aluminum oxide.

[0079] In addition, as a carbon material used as a carrier, a porous carbon material can be preferably cited. The porous carbon material has carbon as the main component. Here, "having carbon as the main component" means that it includes the two concepts of being composed only of carbon and being substantially composed of carbon, and may contain elements other than carbon. "Substantially composed of carbon" means that more than 80% by mass of the whole is composed of carbon, preferably more than 95% by mass of the whole, and more preferably more than 98% by mass of the whole (upper limit: 100% by mass).

[0080] The BET specific surface area of ​​the porous carbon material is not particularly limited. Surprisingly, it was found that the smaller the value of the BET specific surface area of ​​the carrier of the present embodiment, the better. Specifically, the BET specific surface area of ​​the carrier is preferably 3000 m 2 / g or less, more preferably 2000m 2 / g or less, more preferably 1000m 2 / g or less, particularly preferably 500m 2 On the other hand, the lower limit of the BET specific surface area is not particularly limited, but 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 the present embodiment, the carrier has a density of 50 to 3000 m 2 / g of a porous carbon material having a BET specific surface area of ​​1.347 W / m2. With such a structure, an excellent catalytic activity can be exhibited. It should be noted that the BET specific surface area of ​​the porous carbon material can be obtained by the BET method from the measurement results of the nitrogen adsorption and desorption isotherm.

[0081] As a specific example of porous carbon material, for example, graphene mesoporous sponge (GMS), carbon mesoporous sponge (CMS), activated carbon (YP-50F), zeolite template carbon (ZTC), Ketjen Black (Ketjen Black), Vulcan and acetylene black (Denka Black, DB) etc. can be cited. Among them, as porous carbon material, preferably acetylene black, Vulcan, Ketjen Black or activated carbon, more preferably acetylene black or Vulcan. It should be noted that, for the manufacturing method of CMS and GMS, it can be appropriately referred to the previously known content.

[0082] The method for producing the catalyst support of the present embodiment is not particularly limited, and a person skilled in the art can appropriately produce the catalyst support by referring to common technical knowledge in the technical field, except for the part of the examples described below.

[0083] <<Catalysts for gas phase oxidation of organic compounds>>

[0084] As for the catalyst support of one embodiment of the present invention, for example, an organic compound is used for gas phase oxidation. That is, another embodiment of the present invention is a catalyst for gas phase oxidation of organic compounds, which comprises a catalyst support of one embodiment of the present invention. In the past, it was proposed to use the compound as a catalyst to oxidize alcohol in a liquid phase system. However, in the case of a reaction in a liquid phase system, it is necessary to separate the target product and the catalyst from the solvent after the reaction is completed, and further purify the target product, which becomes a problem from the perspective of time and cost. In contrast, the catalyst for gas phase oxidation of organic compounds of this embodiment can achieve oxidation of organic compounds in a gas phase system, and has the advantage that the problems associated with the reaction in a liquid phase system do not occur. It should be noted that for the organic compound to be oxidized by the catalyst for gas phase oxidation of this embodiment, as described later.

[0085] <<Gas Phase Oxidation Method of Organic Compounds>>

[0086] According to another embodiment of the present invention, a method for gas phase oxidation of an organic compound is provided. Specifically, the method is a method for gas phase oxidation of an organic compound, which comprises: in a gas phase in the presence of molecular oxygen, bringing an organic compound having an oxidizable functional group into contact with a catalyst support of one embodiment of the present invention, and oxidizing the oxidizable functional group.

[0087] <Organic compounds>

[0088] In the gas phase oxidation method of this embodiment, the object to be oxidized is an organic compound having an oxidizable functional group. There is no particular limitation on the oxidizable functional group, and examples thereof include a hydroxyl group, a thiol group, and the like, preferably a hydroxyl group. In addition, the oxidation method of this embodiment is carried out in a gas phase system, so the organic compound is preferably a volatile organic compound (VOC). In addition, as the organic compound, alcohols such as primary alcohols and secondary alcohols, thiols, and the like can be mentioned. By the gas phase oxidation method of this embodiment, primary alcohols are oxidized to corresponding aldehydes, secondary alcohols are oxidized to corresponding ketones, and thiols are dimerized and oxidized to corresponding disulfides. Among them, from the viewpoint that the reaction is easy to proceed, the organic compound is preferably an alcohol, and more preferably a primary alcohol or a secondary alcohol.

[0089] <Reaction Conditions>

[0090] Regarding the reaction conditions when implementing the gas phase oxidation method of this mode, if it is in the gas phase in which molecular oxygen exists, there is no particular limitation on other specific compositions. For the "gas phase in which molecular oxygen exists," it can be achieved, for example, by supplying molecular oxygen into the reaction system. In addition, pure oxygen gas can be used as a supply source of molecular oxygen, and the reaction can also be carried out using an oxygen-containing mixed gas or air diluted to an oxygen content of about 5 to 50% by volume by an inactive gas such as nitrogen or carbon dioxide gas. There is no particular limitation on the reaction system, and it can be any of a sealed system, a circulation system, or an open system (in the air).

[0091] As the reaction temperature, it can be constant or variable. In the case of a constant reaction temperature, as the reaction temperature, there is no particular limitation, for example, preferably above 0°C, more preferably above 10°C, further preferably above 15°C, and particularly preferably above 20°C. The reactivity of the oxidation reaction can be improved by a temperature of more than 0°C. On the other hand, as the reaction temperature, it is preferably below 100°C, more preferably below 80°C, further preferably below 50°C, and particularly preferably below 40°C. The degradation of the catalyst support can be suppressed by a reaction temperature of less than 100°C. In addition, when the reaction temperature is varied, the temperature can be raised, lowered, or repeatedly raised and lowered.

[0092] As a reaction device for gas phase oxidation reaction, if the gas as the object can be brought into contact with the catalyst support (catalyst for gas phase oxidation), there is no particular limitation, and any one of a flow reactor, a full batch reactor or a semi-batch reactor can be used. As a flow reactor, for example, a fixed bed atmospheric pressure flow reactor and a fluidized bed reactor can be cited. In a fixed bed atmospheric pressure flow reactor, a fixed layer is used, which fixes a catalyst formed into a granular state. In a fluidized bed reactor, a moving layer is used, which moves the catalyst. From the viewpoint of efficiently bringing the reaction gas into contact with the catalyst, a fixed bed atmospheric pressure flow reactor is preferably used. It should be noted that in the above-mentioned reaction device, the catalyst can be heated from the outside by an electric heater, infrared rays, etc.

[0093] It should be noted that the method for gas phase oxidation of organic compounds using the gas phase oxidation catalyst is not limited to the above embodiment, and for example, the gas phase oxidation catalyst may be arranged on a wind direction louver provided at an air outlet of an air conditioner (air conditioner) of a vehicle, a filter provided in front of the air outlet, etc. According to such a method, organic compounds contained in the air cooled or heated in the air conditioner and discharged from the air outlet can be oxidized. The air discharged from the air conditioner sometimes contains organic compounds (such as alcohol) having a unique odor, and according to the above method, the odor can be reduced by oxidizing such organic compounds.

[0094] <<Catalyst-containing substrate and sprayer>>

[0095] According to another aspect of the present invention, there is provided a catalyst-containing substrate obtained by supporting or coating the catalyst support of one aspect of the present invention on a base substrate. The catalyst support can be conveniently used for various applications using such a catalyst-containing substrate.

[0096] As a base substrate constituting a catalyst-containing substrate, as a material that is relatively cheap and can easily carry and coat a catalyst carrier, for example, woven fabrics, nonwoven fabrics, filters, or urethane foams can be cited. There is no particular limitation on the method of carrying or coating the catalyst carrier on these base substrates. In addition, for example, such a catalyst-containing substrate can be suitably used for masks, medical fiber products, air conditioners, air purifiers, refrigerators, temperature control machines, dehumidifiers, humidifiers, or vacuum cleaner filters. Of course, it can also be used for other purposes.

[0097] In addition, another aspect of the present invention provides a sprayer. The sprayer includes: a spray container and a solution, wherein the solution is contained in the spray container and is a solution in which the catalyst carrier is dispersed. The spray of this aspect can be sprayed to a desired location, thereby oxidizing the organic compound at the location, for example, to exhibit an effect of reducing the odor of the organic compound.

[0098] It should be noted that the following embodiments are also included in the scope of the present invention: the catalyst support according to claim 1 having the features of claim 2; the catalyst support according to claim 1 or 2 having the features of claim 3; the catalyst support according to any one of claims 1 to 3 having the features of claim 4; the catalyst support according to claim 3 or 4 having the features of claim 5; the catalyst support according to any one of claims 1 to 5 having the features of claim 6; the catalyst support according to any one of claims 1 to 6 having the features of claim 7; the catalyst support according to any one of claims 1 to 7 having the features of claim 8; the catalyst support according to any one of claims 1 to 8 having the features of claim 9; the catalyst support according to any one of claims 1 to 8 having the features of claim 10; the catalyst support according to any one of claims 1 to 9 having the features of claim 10; A catalyst carrier according to any one of claims 1 to 10 having the features of claim 1; a catalyst carrier according to any one of claims 1 to 11 having the features of claim 12; a catalyst for gas-phase oxidation of an organic compound comprising the catalyst carrier according to any one of claims 1 to 12; a method for gas-phase oxidation of an organic compound using the catalyst carrier according to any one of claims 1 to 12; a method according to claim 14 having the features of claim 15; a method according to claim 14 or 15 having the features of claim 16; a catalyst-containing substrate using the catalyst carrier according to any one of claims 1 to 12; a catalyst-containing substrate according to claim 17 having the features of claim 18; a catalyst-containing substrate according to claim 17 or 18 having the features of claim 19; a sprayer using the catalyst carrier according to any one of claims 1 to 12.

[0099] Example

[0100] Hereinafter, although an embodiment of the present invention will be described in detail using examples, the technical scope of the present invention is not limited only to the following examples.

[0101] <<Example of Preparation of Catalyst Support>>

[0102] (Preparation of AZADO / GMS, AZADOL / GMS and NHPI / GMS)

[0103] AZADO 5 mg (0.13 mmol) and dichloromethane 100 mL were added to a 300 mL eggplant flask, and AZADO was dissolved by ultrasonication. GMS (SBa-200 source, S BET =1692m 2 / g) 100 mg and dispersed with ultrasound for 30 minutes, then stirred at room temperature for 30 minutes. Then, evaporated to dryness at 40 ° C and 600 hPa using a rotary evaporator, and further vacuum dried for 10 hours to obtain a catalyst support (AZADO / GMS). In addition, as an organic molecular catalyst, in addition to AZADO, 2-azaadamantane-N-hydroxy (AZ ADOL) and N-hydroxyphthalimide (NHPI) that change the nitroxyl radical of AZADO to alcohol are used to prepare catalyst supports (AZADOL / GMS and NHPI / GMS).

[0104] (Preparation of AZADO-metal salt / GMS)

[0105] 0.13 mmol of metal salt (CuI: 25.0 mg, Cu(NO3)2·3H2O: 31.7 mg or Fe(NO3)3·9H2O: 53.1 mg) and 200 mL of water / ethanol (50% by volume each, 200 mL of acetonitrile when CuI is used as the metal salt) were added to a 300 mL eggplant flask and the metal salt was dissolved by ultrasonic wave. 400 mg of GMS as a carrier was added and dispersed by ultrasonic wave for 30 minutes, and then stirred at room temperature for 30 minutes. Then, the mixture was evaporated to dryness at 60°C and 100 hPa (60°C and 250 hPa when acetonitrile was used as the impregnation solution) using a rotary evaporator, and further vacuum dried for 10 hours to obtain metal salt-supported GMS.

[0106] Next, AZADO5mg (0.0328mmol) and dichloromethane 100mL were added to a 300mL eggplant flask and AZADO was dissolved by ultrasonication. The metal salt-supported GMS (CuI / GMS: 102.2mg, Cu(NO3)2 / GMS: 102.5mg, Fe(NO3)3 / GMS: 101.9mg) prepared in advance was added so that the amount of each metal ion was equal to the amount of AZADO, and ultrasonic dispersion was performed for 30 minutes, followed by stirring at room temperature for 30 minutes. Then, the mixture was evaporated to dryness at 40°C and 600hPa using a rotary evaporator, and vacuum dried for 10 hours to obtain catalyst supports (AZADO-CuI / GMS, AZADO-Cu(NO3)2 / GMS, and AZADO-Fe(N O3)3 / GMS) supporting the co-catalyst and AZADO.

[0107] (Preparation of AZADO-Cu(bpy) / GMS)

[0108] Cu(OTf)2 0.03mmol (10.9mg), bpy 0.03mmol (4.7mg) and AZADO 0.03mmol (4.6mg) were added to a 5mL vial and dissolved in 3mL of acetonitrile, and added to a 300mL eggplant-shaped flask to which 90mL of acetonitrile was added. After adding each reagent, the wall of the vial was cleaned with acetonitrile and added to the flask. Next, 100mg of GMS as a carrier was added to the flask and dispersed with ultrasound for 30 minutes, and then stirred at room temperature for 30 minutes. Then, a rotary evaporator was used to evaporate to dryness at 60°C and 250hPa, and further vacuum dried for 10 hours to obtain a catalyst support (AZADO-Cu(bpy) / GMS) loaded with AZADO and a co-catalyst. It should be noted that the coverage of the catalyst support thus obtained is 8%.

[0109] (Preparation of AZADO-Cu(bpy) catalyst supports using various carbon materials and oxides as supports)

[0110] The catalyst support was prepared by the same steps as in the preparation of AZADO-Cu(bpy) / GMS. As the support, the carbon materials used were activated carbon (YP-50F, S B ET =1700m 2 / g), zeolite templated carbon (ZTC, S BET =3790m 2 / g), carbon mesoporous sponge (Carbon mesosponge, CMS, S BET =2150m 2 / g)、Ketjen Black (registered trademark) E C300J (Ketjen Black, KB, S BET =800m 2 / g)、Vulcan(registered trademark)XC-72(VC、S BET =220m 2 / g) and acetylene black (registered trademark) (Denka Black, DB, S BET =68m 2 / g). In addition, silica gel (Wakosil (registered trademark) C-300, S BET =475m 2 / g), fumed silica (S BET =395m 2 / g), alumina (TM-100, S BET =120m 2 / g), titanium oxide (S BET =46m 2 / g), magnesium oxide (S BET =60m 2 / g), cerium oxide (S BET =70m 2 / g) and zeolite (HSZ-320NAA, S BET =660m 2 / g). It should be noted that 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% (alumina), 285% (titania), 219% (magnesia), 187% (cerium oxide) and 20% (zeolite).

[0111] <<Evaluation of Physical Properties of Catalyst Support>>

[0112] [Structural analysis and catalytic activity evaluation of AZADO / GMS]

[0113] (Structural analysis of AZADO / GMS)

[0114] XRD determination

[0115] XRD measurement was performed on the AZADO / GMS prepared above to analyze the structure of the catalyst. In addition, GMS and AZADO were measured in the same manner. The measurement device used was MiniFlex600 manufactured by Rigaku, and the X-ray source used was CuKα radiation. The sample was evenly spread in a circular depression with a diameter of 5 mm on a Si non-reflective sample plate for measurement. The measurement conditions are as follows:

[0116] X-ray tube: Cu

[0117] Tube voltage: 40kV

[0118] Tube current: 15mA

[0119] Slit DS: 1.25deg.

[0120] RS: 13.0mm

[0121] SS: 8.0mm

[0122] Measurement detector: D / tex Ultra

[0123] Sampling width: 0.02deg.

[0124] Scanning speed: 10.0 deg. / min

[0125] Scan axis: 2θ / θ

[0126] Measuring range: 2~60deg.

[0127] The obtained XRD pattern is as follows Figure 2 As shown. In the XRD pattern of GMS, carbon (002) and (10) peaks were observed near 2θ=26° and 44°, respectively. In addition, sharp peaks were observed near 16.2° and 18.7° in the XRD pattern of AZADO. In AZADO / GMS, the same XRD pattern as that of GMS was obtained, indicating that AZADO was highly dispersed on GMS.

[0128] ESR measurement

[0129] The ESR measurement was performed on the AZADO / GMS (2% in Al2O3) prepared as above, and the existence state of AZADO on G MS was analyzed. The 10μM AZADO toluene solution and G MS (2% in Al2O3) were measured in the same way. The measuring device used was JES-X330 manufactured by JEOL. As a powdered catalyst sample, it was diluted to 50 times by mixing with alumina powder using an agate mortar, and 100 mg of it was filled into a quartz / Pyrex (registered trademark) sample tube with an inner diameter of 4mm and a length of 180mm for measurement. AZADO was dissolved in toluene to prepare a 10μM toluene solution, and 600μL was filled into the same sample tube as the powder sample for measurement. The measurement conditions are as follows:

[0130] Sweep magnetic field range: 336±15mT

[0131] Sweep time: 1.0min

[0132] Microwave output power: 1mW

[0133] Time constant: 0.03s

[0134] Modulation magnetic field frequency: 100kHz

[0135] Modulation magnetic field: 0.2mT

[0136] Magnification: 100

[0137] Mn marker insertion amount: 800

[0138] The obtained ESR spectrum is as follows Figure 3As shown. In the ESR spectrum of AZADO toluene solution, three peaks originating from unpaired electrons of AZADO were observed. In addition, in the ESR spectrum of GMS obtained by dilution with alumina, a weaker peak originating from unpaired electrons of GMS was observed. In the ESR spectrum of AZADO / GMS obtained by dilution with alumina, peaks were observed in which the signals believed to be derived from AZADO overlapped with the signals derived from GMS, indicating that AZADO exists as a free radical species on GMS.

[0139] (Evaluation of Catalytic Activity of Gas-Phase Oxidation Reaction of 2-Propanol in Batch System)

[0140] The AZADO / GMS prepared above was used as a catalyst to carry out a gas phase oxidation reaction of 2-propanol at 80°C in a batch system. In addition, the same reaction was carried out for the case where only GMS was used as a catalyst and the case where no catalyst was used (blank). Here, 30 mg of AZADO / GMS and 20 mg of GMS were used. The amount of acetone generated 24 hours after the start of the reaction is as follows: Figure 4 As shown. When AZADO / GMS was used as a catalyst, 0.43 μmol (0.29 μmol based on 20 mg of catalyst) of acetone was observed to be generated 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 amount of acetone generated 24 hours after the start of the reaction was 0.094 μmol and 0.11 μmol, respectively. It can be seen that GMS alone cannot promote the gas phase oxidation reaction of 2-propanol.

[0141] [Structural analysis and catalytic activity evaluation of AZADO-Cu(NO3)2 / GMS]

[0142] (Structural analysis of AZADO-Cu(NO3)2 / GMS)

[0143] XRD determination

[0144] XRD analysis was performed on the AZADO-Cu(NO3)2 / GMS, AZADO-CuI / GMS and AZADO-Fe(NO3)3 / GMS prepared above to analyze the structure of the catalyst. The obtained XRD patterns are as follows: Figure 5As shown. The same pattern as that of GMS was obtained in AZADO-CuI / GMS and AZADO-Fe(NO3)3 / GMS, confirming that AZADO and the metal co-catalyst were highly dispersed on GMS. In AZADO-Cu(NO3)2 / GMS, peaks were observed near 12.7° and 25.6°. However, these peaks did not show consistency with the peaks seen in Cu(NO3)2·3H2O ( Figure 6 ). Therefore, when the obtained XRD pattern was compared with the database, it was confirmed that the two peaks originated from Cu2(NO3)(OH)3(PDF#45-0594)( Figure 6 ). Therefore, it can be seen that Cu2(NO3)(OH)3 is formed on AZADO-Cu(NO3)2 / GMS.

[0145] Elemental analysis

[0146] The AZADO-Cu(NO3)2 / GMS prepared above was subjected to CHN elemental analysis and ICP emission spectrometry analysis to analyze the contents of carbon (C), hydrogen (H), nitrogen (N) and copper (Cu) in the catalyst. Here, it is assumed that GMS is composed only of carbon, and the AZADO and Cu(NO3)2 added during the preparation of the catalyst have all been loaded onto GMS. It should be noted that the analysis equipment for CHN elemental analysis is MICRO CORDER JM10 manufactured by J-SCIENCE LAB. The analysis conditions are as follows:

[0147] Bridge current H: 91mA

[0148] C: 68mA

[0149] N: 125mA

[0150] Furnace temperature SF: 950℃

[0151] CF: 830℃

[0152] RF: 550℃

[0153] Flow rate He: 180mL / min

[0154] O: 17mL / min

[0155] Burn time: 240 seconds

[0156] In addition, as an analytical device for ICP emission spectrometry, an inductively coupled plasma (ICP) emission spectrometer (manufactured by HITACHI HIGH-TECHSCIENCE CO., LTD., SPS-3500 model) was used.

[0157] The results of the above analysis show that about 67% of the added Cu was loaded on GMS from the theoretical values ​​and measured values ​​of the contents of each element calculated from the loading amount. The theoretical amount of N from AZADO is considered to be 0.4 wt%, assuming that nitrate ions (NO 3- ) was loaded as Cu(NO3)2, it was inferred that 100% of the added AZADO was loaded on GMS. In addition, the measured value of H content was greater than the theoretical value, which was inferred to be mainly due to the formation of Cu2(NO3)(OH)3.

[0158] (Evaluation of catalytic activity)

[0159] Gas-phase oxidation of 2-propanol in a batch system

[0160] The AZADO-Cu(NO3)2 / GMS, Cu(NO3)2 / GMS and AZADO / GMS prepared above were used as catalysts, and the gas-phase oxidation reaction of 2-propanol was carried out in a batch system. Specifically, 20 mg of the catalyst support was weighed and placed in a 100 mL reagent bottle, and the bottle was covered with a screw cap dedicated to the dehydrating solvent. Then, O2 containing 1.8 mmol / L of 2-propanol 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 for 24 hours. It should be noted that when AZADO-Cu(bpy) / GMS was used as a catalyst, the same reaction test was carried out using N2 or synthetic air instead of O2. When AZADO / GMS was used as a catalyst, 20 mg of the catalyst was weighed and placed in a 50 mL vial, covered with a septum and wrapped with a sealing film, and then O2 containing 0.7 mmol / L of 2-propanol was introduced at a rate of 50 mL / min for 15 minutes, and the lower part of the vial was immersed in an oil bath at 80°C for 24 hours. When AZADO-Cu(NO3)2 / GMS was used as a catalyst, 20 mg of the catalyst was weighed and placed in a 100 mL reagent bottle, covered with a screw cap for a dehydrating solvent, and then O2 containing 0.7 mmol / L of 2-propanol was introduced at a rate of 50 mL / min for 15 minutes, and the lower part of the reagent bottle was immersed in an oil bath at 80°C or 30°C for 24 hours. It should be noted that when AZADO / GMS and AZADO-Cu(NO3)2 / GMS were used as catalysts, the bubbler was not heated in the oil bath, and only the lower part of the reaction vessel was heated instead of the entire reaction vessel.

[0161] At the beginning of the reaction and after a certain period of time, 1 mL of the reaction gas was collected using a gas-tight syringe and analyzed by gas chromatography. The detector used was a hydrogen flame ionization detector (FID). The reaction conditions and analysis conditions are as follows:

[0162] (Reaction Conditions)

[0163] Catalyst support 80℃: AZADO / GMS 30mg

[0164] : AZADO-Cu(NO3)2 / GMS, Cu(NO3)2 / GMS, AZADO / GMS, GMS 20mg each

[0165] 30℃: AZADO / GMS, AZADO-Cu(NO3)2 / GMS, AZADO-CuI / GMS, AZADO-Cu(bpy) / GMS, TEMPO-Cu(bpy) / GM S, 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, AZADO-Cu(bpy) / silica gel, AZADO-Cu(bpy) / fumed silica, AZADO-Cu(bpy) / A l2O3, AZADO-Cu(bpy) / TiO2, AZADO-Cu(bpy) / MgO, AZADO-Cu(bpy) / CeO2, AZADO-Cu(bpy) / zeolite 20 mg each

[0166] Oxidant O2

[0167] Reaction substrate 2-propanol

[0168] Reaction temperature oil bath 80℃ or 30℃

[0169] Incubator 30℃

[0170] (Analysis conditions)

[0171] [Table 1]

[0172] GC parameters Retention time Column temperature ：85℃ acetone : 2.5 minutes Inlet temperature ：85℃ 2-Propanol : 5.5 minutes Detector temperature ：85℃ Inlet pressure :120kPa Split Ratio ：50.0 Sample volume :1.0mL

[0173] The amount of acetone generated 24 hours after the reaction started at 80°C is as follows Figure 7 As shown. When GMS loaded with GMS and AZADO was used as a catalyst, almost no oxidation reaction was observed. In GMS loaded with only Cu(NO3)2, a small amount of 2.6 μmol of acetone was confirmed to be generated. On the other hand, in AZADO-Cu(NO3)2 / GMS in which both AZADO and Cu(NO3)2 were loaded on GMS, significant acetone generation of 55 μmol was confirmed, and TON was 9.0. From these results, it can be seen that by combining AZADO and a co-catalyst (here, a catalyst containing Cu 2+The Cu(NO3)2) is loaded on the carrier together and synergistically promotes the oxidation reaction.

[0174] The same procedure as above was followed except that the reaction temperature was changed to 30°C. In addition to Cu(NO3)2, AZADO-CuI / GMS with CuI as a co-catalyst was used. Together with AZADO-Cu(NO3)2 / GMS, the reaction was applied to the gas phase oxidation reaction of 2-propanol at room temperature (30°C) and the catalytic activity was compared. The change of TON over time was shown in Figure 8 As shown. When AZADO-Cu(NO3)2 / GMS was used, catalytic acetone production was also confirmed at 30°C. The reaction rate showed a tendency to decrease with the passage of reaction time, and the TON was 7.0 24 hours after the start of the reaction. In addition, catalytic acetone production was also observed in AZADO-CuI / GMS, and the reaction rate showed a roughly constant value. The TON was 3.1 24 hours after the start of the reaction, which was less active than when Cu(NO3)2 was used as a co-catalyst.

[0175] It should be noted that, it is reported that AZADO is used in the reaction in the liquid phase system of the catalyst, and the situation of using copper (I) ion is compared with the situation of using copper (II) ion to obtain higher activity. In contrast, in this reaction, compared with the catalyst of CuI containing copper (I) ion of univalent, the catalyst of Cu (NO containing copper (II) ion of divalent is used. As mentioned above, it is represented that in the gas phase catalyst system, it is possible to react with the reaction mechanism different from the liquid phase system.

[0176] Gas-phase oxidation of 2-propanol in a flow system

[0177] In the reaction at 30°C in the batch system, when AZADO-Cu(NO3)2 / GMS was used as a catalyst, a decrease in the reaction rate due to the rate-limited supply of 2-propanol was observed. Therefore, an excess of 2-propanol was supplied, and the gas phase oxidation reaction of 2-propanol was carried out at 24°C in a flow system for the purpose of studying the durability of the catalyst. Specifically, O2 containing 1.8 mmol / L of 2-propanol was circulated at a rate of 50 mL / min through a glass tube with an outer diameter of 1 / 4 inch into which 20 mg of AZADO-Cu(bpy) / DB was added, and the reaction was carried out for 24 hours in an incubator maintained at a temperature of 30°C. When AZADO-Cu(NO3)2 / GMS was used as a catalyst, 20 mg of the catalyst was used, O2 containing 1.0 mmol / L of 2-propanol was circulated at a rate of 20 mL / min, and the reaction was carried out at room temperature (24°C). When AZADO-Cu(bpy) / GMS was used as a catalyst, 20 mg of the catalyst was used, and O2 containing 1.3 mmol / L of 2-propanol was circulated at a rate of 20 mL / min, and the lower part of the glass tube was immersed in an oil bath at 30°C for 24 hours. At the start of the reaction and after a certain period of time, 1 mL of gas was collected from the downstream of the glass tube using a syringe and analyzed by gas chromatography. A hydrogen flame ionization detector (FID) was used as the detector. The reaction conditions are as follows, and the analysis conditions are the same as above:

[0178] (Reaction Conditions)

[0179] Catalyst support AZADO-Cu(NO3)2 / GMS20mg

[0180] AZADO-Cu(bpy) / GMS20mg

[0181] AZADO-Cu(bpy) / DB 10mg

[0182] Oxidant AZADO-Cu(NO3)2 / GMS, AZADO-Cu(bpy) / GMS O2 flow (20mL / min)

[0183] AZADO-Cu(bpy) / DB O2 flow (50mL / min)

[0184] Reaction substrate 2-propanol

[0185] Reaction temperature AZADO-Cu(NO3)2 / GMS 24℃ (room temperature)

[0186] AZADO-Cu(bpy) / GMS 30℃(Oil bath)

[0187] AZADO-Cu(bpy) / DB 30℃(Incubator)

[0188] The change of the catalyst turnover frequency (TOF) with time when AZADO-Cu(NO3)2 / GMS is used as the catalyst is shown in Fig. 9 As shown. TOF showed 21.2 30 minutes after the start of the reaction, and then decreased rapidly, and decreased to 6.4 1 hour after the start of the reaction. Then TOF decreased slowly and became 2.0 2.5 hours after the start of the reaction. Based on Fig. 9 The calculated TON was 29.2, which was a higher value than the TON (7.0) in the batch system, confirming an improvement in TON.

[0189] [Structural analysis and catalytic activity evaluation of AZADO-Cu(bpy) / GMS]

[0190] (Structural analysis of AZADO-Cu(bpy) / GMS)

[0191] XRD determination

[0192] XRD was performed on the AZADO-Cu(bpy) / GMS prepared as described above to analyze the structure of the catalyst. In addition, Cu(OTf)2 and bpy were similarly measured. As a result, it was confirmed that the XRD pattern of AZADO-Cu(bpy) / GMS was the same as that of GMS, and AZADO, bpy and Cu(OTf)2 were highly dispersed and supported on GMS.

[0193] Elemental analysis

[0194] The prepared AZADO-Cu(bpy) / GMS was subjected to CHN elemental analysis and ICP emission spectrometry to analyze the contents of C, H, N and Cu in the catalyst. Here, it is assumed that GMS is composed only of carbon and that AZADO, Cu(OTf)2 and bpy added during catalyst preparation have all been loaded onto GMS.

[0195] From the theoretical values ​​and measured values ​​of the contents of each element obtained from the loading amount, it can be seen that about 84% of the added Cu has been loaded on GMS, and more Cu can be loaded compared to the case where Cu(NO3)2 is used as a co-catalyst (Cu loading: 67%). Based on the comparison of the N content, it is believed that AZADO has loaded the entire amount.

[0196] (Evaluation of catalytic activity)

[0197] Gas-phase oxidation of 2-propanol in a batch system

[0198] The prepared AZADO-Cu(bpy) / GMS was used as a catalyst to carry out a gas phase oxidation reaction of 2-propanol at 30°C in a batch system. The change of TON over time is shown in FIG. Fig.10 The figure also shows the reaction results of various catalysts used for comparison ( Figure 8 ). The case where AZADO-Cu(bpy) / GMS was used as a catalyst also reacted stably, showing a greater reaction rate than the case where AZADO-Cu(NO3)2 / GMS was used. The reaction rate showed a decreasing tendency, but the TON 24 hours after the start of the reaction was 12.2, showing a higher catalytic activity than the TON (7.0) when AZADO-Cu(NO3)2 / GMS was used as a catalyst. As described above, in AZADO-Cu(NO3)2 / GMS, Cu(NO3)(OH)3 condensed on GMS, while in AZADO-Cu(bpy) / GMS, AZADO and Cu(bpy) were highly dispersed on GMS. Therefore, it can be inferred that the proportion of the surface exposed by Cu in AZADO-Cu(bpy) / GMS increased, thereby improving the catalytic activity.

[0199] Gas-phase oxidation of 2-propanol in a flow system

[0200] In order to study the durability of the catalyst, AZADO-Cu(bpy) / GMS was used as the catalyst to carry out the gas phase oxidation reaction of 2-propanol at 30°C in a flow system. The TOF changes with time are shown in the figure below. Fig.11 As shown. TOF was 17.6 3 minutes after the start of the reaction and then decreased rapidly, and decreased to 2.0 2 hours after the start of the reaction. However, the TOF decreased slowly thereafter, and TOF was 0.9 24 hours after the start of the reaction. Based on Fig.11 The calculated TON was 34.3, which was higher than the TON (12.2) in the batch system, confirming the improvement of TON. Fig.11 The determination coefficient (R 2 ) becomes smaller to 0.4491, so TON is calculated using a function that approximates TOF by power.

[0201] Comparison of catalytic activity between AZADO and TEMPO

[0202] It is expected that the catalyst for gas phase oxidation can promote the oxidation reaction of sterically congested substrates. Therefore, TEMPO-Cu(bpy) / GMS was prepared by using TEMPO as a nitroxyl radical in the same steps as the "Preparation of AZADO-Cu(bpy) / GMS". In addition, the catalyst was applied to the gas phase oxidation reaction of 2-propanol and the gas phase oxidation reaction of ethanol together with AZADO-Cu(bpy) / GMS, and the activities of each catalyst in the two reactions were compared.

[0203] First, when AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS were used as catalysts for gas-phase oxidation of 2-propanol at 30°C in a batch system, the TON at 24 hours after the start of the reaction was as follows: Fig.12 As shown. 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, showing a catalytic activity that was approximately 9 times that of TEMPO as a catalyst for nitroxyl radicals. Thus, it was shown that AZADO-Cu(bpy) / GMS was beneficial for the oxidation of spatially complex alcohols. However, it is known that in conventional liquid phase systems, secondary alcohols cannot be oxidized when TEMPO is used as a catalyst. In contrast, according to the gas phase oxidation of the present invention, it has been confirmed that secondary alcohols can be oxidized even when TEMPO is used as a catalyst.

[0204] Next, AZADO-Cu(bpy) / GMS and TEMPO-Cu(bpy) / GMS were used as catalysts, and a gas-phase oxidation reaction of ethanol was carried out at 30°C in a batch system. Specifically, 20 mg of the catalyst was weighed into a 100 mL reagent bottle and tightly capped with a screw cap for a dehydrated solvent. Then, oxygen containing 2.5 mmol / L of ethanol 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 for 24 hours. 1 mL of the reaction gas was collected using a gastight syringe at the start of the reaction and after a certain period of time, and analyzed by gas chromatography. The reaction conditions and analysis conditions are as follows.

[0205] (Reaction Conditions)

[0206] Catalyst AZADO-Cu(bpy) / GMS, TEMPO-Cu(bpy) / GMS 20 mg each

[0207] Oxidant O2

[0208] Reaction substrate ethanol

[0209] Reaction temperature 30℃ (incubator)

[0210] (Analysis conditions)

[0211] [Table 2]

[0212] GC parameters Retention time Column temperature ：85℃ Acetaldehyde : 1.5 minutes Inlet temperature ：85℃ 2-Propanol : 5.5 minutes Detector temperature ：85℃ Inlet pressure : 120kPa Split Ratio ：50.0 Sample volume :1.0m L

[0213] TON 24 hours after the start of the reaction Fig.13 It can be seen that AZADO-Cu(bpy) / GMS showed a TON of 17 and TEMPO-Cu(bpy) / GMS showed a TON of 6.6 24 hours after the start of the reaction, and that the catalyst using AZADO showed higher activity even when a sterically uncomplex alcohol was used as the substrate.

[0214] Controlled trials

[0215] In order to confirm that the oxidant in the oxidation reaction of 2-propanol is oxygen, N2 containing 2-propanol at 1.8 mmol / L was introduced into the reaction vessel, AZADO-Cu(bpy) / GMS was used as a catalyst, and the reaction was carried out at 30°C for 8 hours in a batch system. The TON at 8 hours after the start of the reaction was as follows: Fig.14 As shown. 8 hours after the start of the reaction, TON was 9.1 in an O2 atmosphere and 1.8 in a N2 atmosphere, and TON was reduced to about one-fifth compared to the reaction in an O2 atmosphere. Thus, it was confirmed that O2 acts as an oxidant in the oxidation reaction of 2-propanol. Here, as the reason why TON does not become 0 even in an N2 atmosphere, it is believed that the replacement of the air inside the reaction container with N2, the mixing of air when N2 is introduced, and the mixing of air due to the decrease in the internal pressure of the reaction container accompanying the collection of gas samples. In addition, it is believed that in the absence of O2, AZADO or AZADO + The oxidation reaction occurs, and TON shows a maximum of 1. In this experiment, it is estimated that TON does not become 0 in the N2 atmosphere due to the contribution of these two factors.

[0216] In addition, synthetic air containing 1.8 mmol / L of 2-propanol was introduced into the reaction vessel, and AZA DO-Cu(bpy) / GMS was used as a catalyst. When the reaction was carried out at 30°C for 24 hours in a batch system, the change of TON over time was as follows: Fig.15As shown. As a result, the reaction rate was slower than when O2 was used, but the reaction was also stable when synthetic air was used. TON 24 hours after the start of the reaction was 7.9, which was about 65% of the value when O2 was used (TON 12.2). It was confirmed that the proportion of O2 contained in synthetic air was about one-fifth of pure O2, and 65% of the activity was obtained when pure O2 was introduced, and the oxidation reaction was fully promoted even in air.

[0217] [Structural Analysis and Catalytic Activity Evaluation of AZADO-Cu(bpy)-based Catalysts Using Various Carbon Materials and Oxides as Supports]

[0218] (Structural analysis of AZADO-Cu(bpy)-based catalysts based on XRD measurement)

[0219] The catalysts prepared by loading AZADO and Cu(bpy) on various carbon materials and oxides were analyzed by XRD measurement. As a result, it was confirmed that the XRD pattern of any catalyst was the same as that of the carbon material used, and that AZADO and Cu(bpy) were loaded on each carrier in a highly dispersed manner.

[0220] Furthermore, in the XRD patterns of the catalysts prepared using various oxide supports, the same patterns as those of the oxide supports used were obtained for all the catalysts, confirming that AZADO and Cu(b py) were supported on each support in a highly dispersed manner.

[0221] (Evaluation of catalytic activity)

[0222] Gas-phase oxidation of 2-propanol in a batch system

[0223] When the 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, the time-dependent changes in TON obtained for the catalysts using various carbon materials as supports were as follows: Fig.16As shown. The TON of the case where AZADO-Cu(bpy) / GMS, AZ ADO-Cu(bpy) / YP-50F, AZADO-Cu(bpy) / KB and AZADO-Cu(bpy) / VC were used as catalysts showed roughly the same behavior until 2 hours after the start of the reaction, and decreased as the reaction time passed. Then, in the catalysts using YP-50F and KB as carriers, the reaction rate decreased by roughly the same amount, and the TON 24 hours after the start of the reaction was 16 and 15, respectively. In the catalyst using GMS as a carrier, the decrease in reaction rate was greater than that of the catalyst using YP-50F and KB as a carrier, and the TON 24 hours after the start of the reaction was 12. On the other hand, in the catalyst using VC as a carrier, the decrease in reaction rate was almost not observed, and the TON 24 hours after the start of the reaction was a high value of 28. In AZADO-Cu(bpy) / DB, the initial reaction rate was the largest, and the same decrease in reaction rate as in the case where VC was used as a carrier was hardly observed. The TON at 24 hours after the start of the reaction showed the highest value of 34. In AZADO-Cu(bpy) / CMS, the reaction rate up to 4 hours after the start of the reaction was less than half of the catalyst using GMS, YP-50F, KB, VC, and DB as carriers, and the reaction rate after 4 hours did not decrease but remained approximately constant, and the TON at 24 hours after the start of the reaction was 10. It should be noted that the reaction was carried out in AZADO-Cu(bpy) / ZTC, but the TON at 24 hours after the start of the reaction showed a lower value of 0.6.

[0224] Next, the time-dependent changes in TON obtained by using various oxides as supported catalysts are shown in FIG. Fig.17As shown. In AZADO-Cu(bpy) / MgO, the reaction proceeded but the reaction rate was slow, and the TON 24 hours after the start of the reaction was 1. In AZADO-Cu(bpy) / TiO2, the initial reaction rate was the smallest, but the reaction continued very slowly, and the TON 24 hours after the start of the reaction was 2. In the catalysts using AZADO-Cu(bpy) / silica gel and AZADO-Cu(bpy) / fumed silica as supports, the reaction continued slowly, and the TON 24 hours after the start of the reaction was 7 and 6, respectively. In AZADO-Cu(bpy) / Al2O3, the reaction started to proceed rapidly. Then the reaction rate decreased exponentially, but the TON 24 hours after the start of the reaction showed the highest value of 20. The TON in the case of using AZADO-Cu(bpy) / zeolite also showed the same tendency as the catalyst using Al2O3 as a support, and the TON 24 hours after the start of the reaction showed a relatively high value of 14. In AZADO-Cu(bpy) / CeO2, the initial reaction rate is smaller than that of the case where zeolite is used as a carrier, but there is almost no decrease in the reaction rate. The TON 24 hours after the start of the reaction exceeds that of the case where zeolite is used as a carrier and is shown as 17, which is a higher value second only to the case where Al2O3 is used as a carrier. The reason why the catalyst using Al2O3 as a carrier shows a higher catalytic activity is considered to be the promotion of the oxidation reaction based on the generation of oxoammonium ions. As mentioned above, nitroxyl radicals are oxidized to generate oxoammonium ions. In addition, Al2O3 is known to have solid acidity. It is speculated that the disproportionation reaction of AZADO occurs through the solid acidity of Al2O3, and the generated oxoammonium ions promote the oxidation reaction. It is believed that when CeO2 is used as a carrier, there is a possibility that the oxidation reaction is promoted by the redox reaction of Ce.

[0225] Research on carrier effect

[0226] In the above study, it was shown that the gas phase oxidation reaction of 2-propanol using catalysts with AZADO and Cu(b py) supported on various carbon materials had different catalytic activities depending on the carbon material used as a carrier. Therefore, a scatter plot was made for the specific surface area, total pore volume, edge volume, 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 studied. The obtained scatter plot is as follows: Fig.18 When a scatter plot of TON is drawn against the specific surface area, the R 2 The value is 0.8585, indicating a strong negative correlation between these ( Fig.18(a)). From this, it is inferred that AZAD O and Cu(bpy) can exist close to each other on a carbon support with a low specific surface area, which can efficiently promote the oxidation reaction and obtain a larger TON. This is contrary to the common sense that the larger the specific surface area of ​​a catalyst support, the more favorable the catalytic activity. In addition, when a scatter plot of TON is drawn relative to the total pore volume, R 2 The value is 0.2108, which shows that there is almost no correlation between these values ​​( Fig.18 (b)). It can be seen that when a scatter plot is drawn for TO N relative to the edge amount, R 2 The value is 0.5779, and a weak negative correlation is observed, but it is smaller than the correlation between specific surface area and TON ( Fig.18 (c)). In addition, when a scatter plot of TON is plotted against the spin density, R 2 The value is 0.6612, which shows that there is a relatively strong negative correlation ( Fig.18 (d)).

[0227] The above studies show that the activity of the catalyst using carbon materials as carriers is strongly negatively correlated with the specific surface area of ​​each carbon material. Therefore, the TON 24 hours after the start of the reaction obtained using catalysts using various oxides as carriers was sorted by the specific surface area of ​​each oxide and compared with the case where a carbon carrier was used. The scatter plot of TON 24 hours after the start of the reaction relative to the specific surface area of ​​each oxide carrier is shown in Figure 1. Fig.19 Here, Fig.19 The scatter plots of the cases where various carbon carriers were used are also shown. From the obtained scatter plots, it can be seen that the case where any oxide carrier was used showed lower activity than the case where a carbon carrier with the same specific surface area was used. The results show that in the present catalyst system using a solid catalyst loaded with AZADO and Cu(bpy), a carrier containing carbon materials is particularly useful. Among them, when acetylene black was used as a carrier, the TON was 36, and the highest catalytic activity was obtained. It is speculated that this is because the specific surface area of ​​acetylene black is smaller at 68m 2 / g, AZADO and Cu(bpy) can exist close to each other.

[0228] The results shown above indicate that, according to the present invention, nitroxyl radicals can be used as catalysts to oxidize organic compounds in the gas phase.

[0229] 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. A catalyst support, which is obtained by supporting a compound having the following redox mechanism and a co-catalyst containing a transition metal on a support, [Chemical formula 1] Where, X - For counter anions, dashed lines indicate bonding sites to other atoms.

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

3. The catalyst support according to claim 1, wherein The nitroxyl radical form of the compound is shown in the following compound formula 1: [Chemical formula 2] [Compound Formula 1] In the formula, R1 to R4, Y1 and Y2 are each independently a hydrogen atom or an optionally substituted monovalent organic group, wherein: Y1 and Y2 are optionally bonded to each other to form a nitrogen-containing monocyclic ring containing a 5-membered ring or a 6-membered ring which is optionally substituted, and R1 and R3 are optionally bonded to each other to form an optionally substituted 5-membered or 6-membered nitrogen-containing bicyclic ring, or two rings constituting the nitrogen-containing bicyclic ring are optionally further cross-linked to form an optionally substituted 5-membered or 6-membered nitrogen-containing tricyclic ring.

4. The catalyst support according to claim 3, wherein The nitroxyl radical form of the compound is shown in the following compound formula 2: [Chemical formula 3] [Compound Formula 2] In the formula, R1 to R4 are independently a hydrogen atom or an optionally substituted monovalent organic group, Z is an optionally substituted 5-membered or 6-membered nitrogen-containing monocyclic ring, wherein further optionally R1 and R3 are bonded to each other to form a nitrogen-containing bicyclic ring containing a 5-membered ring or a 6-membered ring which may be substituted, or two rings constituting the nitrogen-containing bicyclic ring are further cross-linked to form a nitrogen-containing tricyclic ring containing a 5-membered ring or a 6-membered ring which may be substituted.

5. The catalyst support according to claim 3 or 4, wherein When the compound does not contain the monocyclic ring, the bicyclic ring or the tricyclic ring, or contains the nitrogen-containing monocyclic ring, R1 to R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, When the compound includes the nitrogen-containing bicyclic ring or the nitrogen-containing tricyclic ring, R2 and R4 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

6. 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 compounds: [Chemical formula 4-1] [Chemical formula 4-2] 7. The catalyst support according to claim 6, wherein The nitroxyl radical form of the compound is 2-azaadamantane-N-oxyl (AZADO).

8. The catalyst support according to claim 1 or 2, wherein The transition metal includes one or more selected from Ag, Au, Pt, Pd, Ni, Mn, Fe, Ti, Al, Zn and Cu.

9. The catalyst support according to claim 8, wherein The transition metal includes Cu.

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

11. The catalyst support according to claim 1 or 2, wherein The coverage rate of the compound and the promoter in the surface area of ​​the carrier is 10 to 300%.

12. The catalyst support according to claim 1 or 2, wherein The carrier has 50 to 3000 m 2 Porous carbon material with a BET specific surface area of ​​ / g. 13 . A catalyst for gas-phase oxidation of an organic compound, comprising the catalyst support according to claim 1 or 2.

14. A method for gas phase oxidation of an organic compound, comprising: An organic compound having an oxidizable functional group is brought into contact with the catalyst support according to claim 1 or 2 in a gas phase in the presence of molecular oxygen to oxidize the oxidizable functional group.

15. The gas phase oxidation method according to claim 14, wherein: The organic compound is a volatile organic compound.

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

17. A catalyst-containing substrate obtained by supporting or coating the catalyst support according to claim 1 or 2 on a base substrate.

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

19. The catalyst-containing substrate according to claim 17, which is used for a mask, a medical fiber product, an air conditioner, an air purifier, a refrigerator, a temperature control machine, a dehumidifier, a humidifier, or a filter for a vacuum cleaner.

20. A sprayer comprising: Aerosol containers; and A solution contained in the spray container and in which the catalyst support according to claim 1 or 2 is dispersed.

Images