CN111847474A - Ti-ITQ-24 zeolite molecular sieve and in-situ synthesis method and application thereof - Google Patents
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Abstract
The invention relates to the field of zeolite molecular sieves, and provides a Ti-ITQ-24 zeolite molecular sieve, wherein a framework only contains two tetravalent elements of Ti and Si. The in-situ synthesis method is also provided for the first time: uniformly mixing a silicon source, a titanium source, an organic template agent OSDA, a fluorine source and water to obtain a mixture, wherein the titanium source is selected from titanium sulfate, amorphous titanium dioxide, tetrabutyl titanate and a titanium-containing molecular sieve, and the OSDA is 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt; performing hydrothermal crystallization at the temperature of 140-180 ℃ for 2-8 days to obtain a crystallized product; the crystallized product is then washed, separated, dried and calcined. The Ti utilization rate is high, Ge doping and the like are not needed to stabilize the framework, and the cost is reduced. Also provides the application of the Ti-ITQ-24 zeolite molecular sieve as a catalyst for industrial oxidation reaction.
Description
Technical Field
The invention relates to the field of zeolite molecular sieves, in particular to a Ti-ITQ-24 zeolite molecular sieve and an in-situ synthesis method and application thereof.
Background
The porous zeolite molecular sieve material has excellent shape-selective catalytic ability in the fields of petrochemical industry, environmental pollution elimination and the like due to the unique framework and pore channel structure.
Corma et al, 2003, disclosed a method for obtaining a silicon-germanium-aluminum molecular sieve ITQ-24 synthesized using a hexamethylenebis (trimethylammonium) dicationic template (J. Am. chem. Soc., 2003,125, 7820-7821 and US7344696B) using a dual-quaternary ring structure in a Ge-stabilized framework. The ITQ-24 molecular sieve is an IWR topological structure and has a twelve-membered ring and ten-membered ring cross channel structure. The molecular sieve with the pore structure has excellent catalytic performance in aromatic alkylation reaction. Thereafter, Yang et al disclosed a method for synthesizing ITQ-24 using diethyldimethylammonium hydroxide as an organic template (CN 107954440A), and introduced other heteroatoms in the backbone. The silicon-aluminum type ITQ-24 is successfully synthesized by the Zhongfengshou group in 2019 for the first time, the limitation that the ITQ series needs Ge-doped stable frameworks is broken, and the silicon-aluminum type ITQ-24 has great industrial application prospect.
The titanium silicalite TS-1 has wide industrial application, and particularly shows excellent catalytic performance in selective oxidation reaction with dilute hydrogen peroxide as an oxidant. This relies primarily on the catalytic action of Ti in the framework, and so the preparation of Ti-containing molecular sieves has been of interest. In comparison, the ITQ-24 has a twelve-membered ring and ten-membered ring cross channel structure, and is more beneficial to the passing of organic macromolecular species after Ti is introduced, so that the mass transfer efficiency of the system is improved, and the oxidation performance is improved. To date, there have been no cases of successful in situ synthesis reported.
Disclosure of Invention
The invention provides a Ti-ITQ-24 zeolite molecular sieve which has a stable structure, and the framework only contains two tetravalent elements of Ti and Si; the in-situ synthesis method of the Ti-ITQ-24 zeolite molecular sieve is also provided, the preparation steps are simple, the Ti utilization rate is high, doping is not needed, and the synthesis cost is low; also provides the application of the Ti-ITQ-24 zeolite molecular sieve as a catalyst for industrial oxidation reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Ti-ITQ-24 zeolite molecular sieve contains only two kinds of quadrivalent elements of Ti and Si in its skeleton. The ITQ-24 has a twelve-membered ring and ten-membered ring cross channel structure, and is more beneficial to the passing of organic macromolecular species after Ti is introduced, so that the mass transfer efficiency of the system is improved, and the oxidation performance is improved.
The in-situ synthesis method of the Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) uniformly mixing a silicon source, a titanium source, an organic template agent OSDA, a fluorine source and water to obtain a mixture, wherein the mixing molar ratio is as follows: in silicon sourceSiO of (2)2OSDA F of fluorine source-:H2O is 1 (0.1-1.0) to 0.1-1.0 (1-5), the molar ratio of the titanium source and the silicon source is that Ti/Si is less than or equal to 1/15, wherein the titanium source is selected from titanium sulfate, amorphous titanium dioxide, tetrabutyl titanate and titanium-containing molecular sieve, OSDA is 1,1' - [1, 4-phenylene-bis (methylene) ]Bis (1-methylpiperidine) onium salt;
(2) performing hydrothermal crystallization on the mixture at the temperature of 140-180 ℃ for 2-8 days to obtain a crystallized product;
(3) and washing, separating, drying and calcining the crystallized product to obtain the Ti-ITQ-24 zeolite molecular sieve.
The method introduces Ti into the all-silicon ITQ-24 framework in situ for the first time, has high Ti utilization rate, does not need Ge doping and the like to stabilize the framework, and reduces the synthesis cost. Compared with an impregnation method or an ion exchange method, the Ti-ITQ-24 molecular sieve prepared by the method has a more stable structure. The Ti/Si can be adjusted by adjusting the titanium content in the raw materials, so that the requirements of different catalytic reactions can be met. The synthesis steps are simple, and the catalytic application is convenient.
Preferably, the synthesis of 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salts comprises the steps of:
1) dissolving p-dibromide benzyl in an organic solvent, and dropwise adding N-methylpyrrolidine to obtain a mixed solution, wherein the molar ratio of the p-dibromide benzyl to the N-methylpyrrolidine is 2.5, and the organic solvent is selected from one or more of acetonitrile, ethanol and methanol; preferably acetonitrile;
2) heating and refluxing the mixed solution at 80 ℃ for 36-48 h to obtain a solid product;
3) washing, separating and vacuum drying the product to obtain bromine salt;
4) The above bromine salt is exchanged with an anion resin in the hydroxide form to convert it into a 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt in the hydroxide form.
Preferably, the titanium source and the silicon source are Ti-MWW or Ti-MFI, and the Ti/Si in the Ti-MWW or Ti-MFI is less than or equal to 1/15. Ti-MWW or Ti-MFI can be used as a titanium source and a silicon source at the same time.
Preferably, the moles of silicon source and OSDA as organic template agentRatio of SiO2OSDA =1 (0.15-0.5). The crystallinity of the product is better at the preferred molar ratio.
Preferably, the molar ratio of the silicon source to the water is SiO2:H2O =1 (1-3). The molar ratio of the silicon source to the water is SiO2:H2When O =1 (3-5), the mixture is dried at 20-50 ℃ for excessive moisture to form SiO2:H2O is in the range of 1 to 3.
Preferably, the molar ratio of the silicon source to the fluorine source is SiO2:F-And (0.2-0.5), wherein the fluorine source is one of hydrofluoric acid, ammonium fluoride and ammonium bifluoride.
Preferably, the mixture in the step (2) is subjected to hydrothermal crystallization at 150-170 ℃ for 3-7 days.
The invention also provides an application of the Ti-ITQ-24 zeolite molecular sieve as an industrial oxidation reaction catalyst.
Therefore, the invention has the following beneficial effects: the method introduces Ti into the all-silicon ITQ-24 framework in situ for the first time, has high Ti utilization rate, does not need Ge doping and the like to stabilize the framework, and reduces the synthesis cost. Compared with an impregnation method or an ion exchange method, the Ti-ITQ-24 molecular sieve prepared by the method has a more stable structure. The Ti/Si can be adjusted by adjusting the titanium content in the raw materials, so that the requirements of different catalytic reactions can be met. The synthesis steps are simple, and the catalytic application is convenient.
Drawings
FIG. 1 is an X-ray (XRD) diagram of the synthesis of Ti-ITQ-24 using Ti-MWW as a solid titanium and silicon source in example 1.
FIG. 2 is a scanning image (SEM) of the synthesis of Ti-ITQ-24 in example 1 using Ti-MWW as the solid titanium and silicon source.
FIG. 3 is the solid UV spectrum of the sample synthesized by Ti-ITQ-24 in example 1 with Ti-MWW as the solid Ti and Si source after calcination.
FIG. 4 is an X-ray (XRD) diagram of the synthesis of Ti-ITQ-24 from example 8 using Ti-MFI as the solid titanium and silicon source.
FIG. 5 is a scanning image (SEM) of the synthesis of Ti-ITQ-24 from example 8 using Ti-MFI as the solid titanium and silicon source.
FIG. 6 is a solid UV spectrum of a sample synthesized by Ti-ITQ-24 in example 8 with Ti-MFI as the solid titanium and silicon source after calcination.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.
The invention provides a Ti-ITQ-24 zeolite molecular sieve containing only two tetravalent elements of Ti and Si in a framework, which can be used as an industrial oxidation reaction catalyst and a preparation method thereof is shown in the following embodiments.
Example 1
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MWW, organic template agent OSDA, hydrofluoric acid and water are mixed according to a molar ratio SiO2:OSDA:F-:H2Mixing O =1:0.25:0.5:2 uniformly to obtain a mixture, wherein the ratio of Ti/Si in the Ti-MWW skeleton is 1/15 smaller, and the specific numerical value can be adjusted according to the requirement of Ti/Si in the product skeleton, and the following steps are carried out; OSDA is 1,1' - [1, 4-phenylenebis (methylene)]The bis (1-methylpiperidine) onium salt is synthesized by the following steps:
1) dissolving p-dibromide benzyl in acetonitrile, and dropwise adding N-methylpyrrolidine to obtain a mixed solution, wherein the molar ratio of the p-dibromide benzyl to the N-methylpyrrolidine is 2.5;
2) heating and refluxing the mixed solution at 80 ℃ for 40 h to obtain a solid product;
3) washing, separating and vacuum drying the product to obtain bromine salt;
4) converting the bromide salt into 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt in hydroxide form by exchanging with anion resin in hydroxide form; titrating the solution obtained by exchanging with oxyhydrogen type anion resin by using an HCl solution, and calculating to obtain that the exchange yield of anions reaches over 90 percent;
wherein, the steps 3) and 4) are the prior art, and are not specifically explained, and the following is the same;
(2) Putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a drying oven at 150 ℃ for crystallization for 5 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24. The XRD pattern is shown in fig. 1, showing a characteristic IWR framework structure. The SEM is shown in FIG. 2 as a 1 micron size rectangular solid crystal. The ultraviolet spectrum is shown in FIG. 3, which shows that the sample has no external TiO of the skeleton2。
Example 2
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) titanium sulfate, amorphous silicon dioxide, organic template agent OSDA, hydrofluoric acid and water are mixed according to the molar ratio of Ti to SiO2:OSDA:F-:H2O = (1/15) 1:0.1:0.3:5, and mixing uniformly to obtain a mixture; OSDA is 1,1' - [1, 4-phenylenebis (methylene)]The bis (1-methylpiperidine) onium salt is synthesized by the following steps:
1) dissolving p-dibromide benzyl in acetonitrile, and dropwise adding N-methylpyrrolidine to obtain a mixed solution, wherein the molar ratio of the p-dibromide benzyl to the N-methylpyrrolidine is 2.5;
2) heating and refluxing the mixed solution at 80 ℃ for 36 hours to obtain a solid product;
3) washing, separating and vacuum drying the product to obtain bromine salt;
4) Converting the bromide salt into 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt in hydroxide form by exchanging with anion resin in hydroxide form; titrating the solution obtained by exchanging with oxyhydrogen type anion resin by using an HCl solution, and calculating to obtain that the exchange yield of anions reaches over 90 percent;
(2) drying the mixture at 20 deg.C to remove excessive water to obtain SiO2:H2O is in the range of 1 to 3, then the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in an oven at 170 ℃ for crystallization for 4 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 3
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MWW, organic template agent OSDA, hydrofluoric acid and water are mixed according to a molar ratio SiO2:OSDA:F-:H2O =1:0.15:0.1:1 to obtain a mixture, wherein OSDA is 1,1' - [1, 4-phenylenebis (methylene)]The bis (1-methylpiperidine) onium salt is synthesized by the following steps:
1) dissolving p-dibromide benzyl in acetonitrile, and dropwise adding N-methylpyrrolidine to obtain a mixed solution, wherein the molar ratio of the p-dibromide benzyl to the N-methylpyrrolidine is 2.5;
2) Heating the mixed solution at 80 ℃ for reflux reaction for 48 hours to obtain a solid product;
3) washing, separating and vacuum drying the product to obtain bromine salt;
4) converting the bromide salt into 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt in hydroxide form by exchanging with anion resin in hydroxide form; titrating the solution obtained by exchanging with oxyhydrogen type anion resin by using an HCl solution, and calculating to obtain that the exchange yield of anions reaches over 90 percent;
(2) putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a drying oven at 140 ℃ for crystallization for 8 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 4
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MWW, organic template agent OSDA, ammonium fluoride and water are mixed according to a molar ratio SiO2:OSDA:F-:H2O =1:1:1:3 to obtain a mixture, wherein the OSDA is 1,1' - [1, 4-phenylenebis prepared as in example 1(methylene group)]Bis (1-methylpiperidine) onium salt;
(2) putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a drying oven at 180 ℃ for crystallization for 2 days;
(3) Washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 5
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) amorphous titanium dioxide, amorphous silicon dioxide, organic template agent OSDA, hydrofluoric acid and water are mixed according to the molar ratio of Ti to SiO2:OSDA:F-:H2O = (1/50) 1:0.25:0.5:5, and mixing uniformly to obtain a mixture; OSDA is 1,1' - [1, 4-phenylenebis (methylene) prepared in example 1]Bis (1-methylpiperidine) onium salt;
(2) drying the mixture at 50 deg.C to remove excessive water to obtain SiO2:H2O is in the range of 1 to 3, then the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in a drying oven at the temperature of 140 ℃ for crystallization for 5 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 6
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) tetrabutyl titanate, amorphous silicon dioxide, organic template agent OSDA, hydrofluoric acid and water according to the molar ratio of Ti to SiO 2:OSDA:F-:H2O = (1/20) and 1:1:0.8:1 are mixed evenly to obtain a mixture; OSDA is 1,1' - [1, 4-phenylenebis (methylene) prepared in example 1]Bis (1-methylpiperidine) onium salt;
(2) putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a 180 ℃ oven for crystallization for 3 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 7
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MFI, organic template agent OSDA, ammonium bifluoride and water are mixed according to the molar ratio SiO2:OSDA:F-:H2Mixing O =1:1:1:3 uniformly to obtain a mixture, wherein the Ti/Si ratio of Ti-MFI is 1/15, and the specific value can be adjusted according to the Ti/Si requirement in the product framework, and the following steps are the same; OSDA is 1,1' - [1, 4-phenylenebis (methylene) prepared in example 1]Bis (1-methylpiperidine) onium salt;
(2) drying the mixture at 40 deg.C to remove excessive water to obtain SiO2:H2O is in the range of 1 to 3, then the mixture is put into a crystallization kettle with a polytetrafluoroethylene lining and is placed in a 160 ℃ oven for crystallization for 6 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 8
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MFI, organic template agent OSDA, ammonium bifluoride and water are mixed according to the molar ratio SiO2:OSDA:F-:H2O =1:0.25:0.5:2 to obtain a mixture, wherein the OSDA is 1,1' - [1, 4-phenylenebis (methylene) prepared in example 1]Bis (1-methylpiperidine) onium salt;
(2) putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a drying oven at 160 ℃ for crystallization for 5 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24. The XRD pattern is shown in fig. 4, showing a characteristic IWR framework structure. The SEM is shown in FIG. 5 as a 1 micron size rectangular solid crystal. The ultraviolet spectrum is shown in FIG. 6, which shows that the sample has no external TiO of the skeleton2。
Example 9
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MFI, organic template agent OSDA, ammonium bifluoride and water are mixed according to the molar ratio SiO2:OSDA:F-:H2O =1:0.5:0.8:3 to obtain a mixture, wherein the OSDA is 1,1' - [1, 4-phenylenebis (methylene) prepared in example 1]Bis (1-methylpiperidine) onium salt;
(2) Putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a drying oven at 180 ℃ for crystallization for 4 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Example 10
An in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve comprises the following steps:
(1) Ti-MFI, organic template agent OSDA, ammonium bifluoride and water are mixed according to the molar ratio SiO2:OSDA:F-:H2O =1:0.8:0.2:1 to obtain a mixture, wherein the OSDA is 1,1' - [1, 4-phenylenebis (methylene) prepared in example 1]Bis (1-methylpiperidine) onium salt;
(2) putting the mixture into a crystallization kettle with a polytetrafluoroethylene lining, and placing the crystallization kettle in a drying oven at 140 ℃ for crystallization for 7 days;
(3) washing the crystallized product with distilled water, separating, drying at 100 deg.C to obtain solid powder, and calcining at 550 deg.C for 6 hr to obtain white solid powder of Ti-ITQ-24.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. A Ti-ITQ-24 zeolite molecular sieve is characterized in that the framework only contains two framework quadrivalent elements of Ti and Si.
2. A method of in situ synthesis of a Ti-ITQ-24 zeolite molecular sieve according to claim 1, comprising the steps of:
(1) uniformly mixing a silicon source, a titanium source, an organic template agent OSDA, a fluorine source and water to obtain a mixture, wherein the mixing molar ratio is as follows: SiO in silicon source2OSDA F of fluorine source-:H2O is 1 (0.1-1.0) to 0.1-1.0 (1-5), the molar ratio of the titanium source and the silicon source is that Ti/Si is less than or equal to 1/15, wherein the titanium source is selected from titanium sulfate, amorphous titanium dioxide, tetrabutyl titanate and titanium-containing molecular sieve, OSDA is 1,1' - [1, 4-phenylene-bis (methylene)]Bis (1-methylpiperidine) onium salt;
(2) performing hydrothermal crystallization on the mixture at the temperature of 140-180 ℃ for 2-8 days to obtain a crystallized product;
(3) and washing, separating, drying and calcining the crystallized product to obtain the Ti-ITQ-24 zeolite molecular sieve.
3. The in-situ synthesis method of a Ti-ITQ-24 zeolite molecular sieve as claimed in claim 2, wherein the synthesis method of 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt comprises the following steps:
1) dissolving p-dibromide benzyl in an organic solvent, and dropwise adding N-methylpyrrolidine to obtain a mixed solution, wherein the molar ratio of the p-dibromide benzyl to the N-methylpyrrolidine is 2.5, and the organic solvent is selected from one or more of acetonitrile, ethanol and methanol;
2) Heating and refluxing the mixed solution at 80 ℃ for 36-48 h to obtain a solid product;
3) washing, separating and vacuum drying the product to obtain bromine salt;
4) the above bromine salt is exchanged with an anion resin in the hydroxide form to convert it into a 1,1' - [1, 4-phenylenebis (methylene) ] bis (1-methylpiperidine) onium salt in the hydroxide form.
4. The in-situ synthesis method of the Ti-ITQ-24 zeolite molecular sieve of claim 2, wherein the silicon source and the titanium source are Ti-MWW or Ti-MFI, and Ti/Si in the Ti-MWW or Ti-MFI is not more than 1/15.
5. The in-situ synthesis method of Ti-ITQ-24 zeolite molecular sieve of claim 2, wherein the molar ratio of silicon source to organic template agent OSDA is SiO2:OSDA =1:(0.15~0.5)。
6. The in-situ synthesis method of Ti-ITQ-24 zeolite molecular sieve of claim 2, wherein the molar ratio of silicon source and water is SiO2:H2O =1:(1~3)。
7. The in-situ synthesis method of Ti-ITQ-24 zeolite molecular sieve of claim 2, wherein the molar ratio of silicon source and fluorine source is SiO2:F-And (0.2-0.5), wherein the fluorine source is one of hydrofluoric acid, ammonium fluoride and ammonium bifluoride.
8. The in-situ synthesis method of the Ti-ITQ-24 zeolite molecular sieve as claimed in claim 2, wherein the mixture in the step (2) is hydrothermally crystallized at 150-170 ℃ for 3-7 days.
9. Use of the zeolite molecular sieve of Ti-ITQ-24 of claim 1 as a catalyst for industrial oxidation reactions.
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