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KR-20260065282-A - CATALYST FOR OXYGEN REDUCTION REACTION, MANUFACTURING METHOD THEREOF

KR20260065282AKR 20260065282 AKR20260065282 AKR 20260065282AKR-20260065282-A

Abstract

The present invention comprises the steps of mixing and grinding a titanium metal-organic framework and melamine, and The invention relates to a method for preparing a catalyst for an oxygen reduction reaction comprising the step of pyrolyzing a ground mixture at 800°C or higher and 1100°C or lower, a titanium metal-organic framework prepared according to the method, and a catalyst for an oxygen reduction reaction comprising TiN, Ti³⁺ , and Ti⁴⁺ dispersed in the titanium metal-organic framework, thereby providing a catalyst for an oxygen reduction reaction having excellent hydrogen peroxide production efficiency and Faraday efficiency.

Inventors

  • 김진수
  • 팜민토안
  • 임경민

Assignees

  • 경희대학교 산학협력단

Dates

Publication Date
20260508
Application Date
20241101

Claims (9)

  1. Titanium metal-organic framework; and A catalyst for an oxygen reduction reaction comprising TiN, Ti³⁺ , and Ti⁴⁺ dispersed in the above titanium metal-organic framework.
  2. In paragraph 1, A catalyst for an oxygen reduction reaction having a ratio of the Ti 3+ peak area to the Ti 4+ peak area according to XPS analysis of 0.7 or greater.
  3. In paragraph 1, A catalyst for an oxygen reduction reaction having a ratio of the TiN peak area to the total area of 10% or more according to Ti 2p XPS analysis.
  4. In paragraph 1, The above titanium metal-organic framework is one or more selected from the group consisting of MIL125- NH2 , MIL-100 (Ti), MIL-101 (Ti), MIL-167, MIL-168, MIL-169, MOF-901, MOF-902 and combinations thereof, a catalyst for an oxygen reduction reaction.
  5. A step of mixing and grinding titanium metal-organic framework and melamine; and A method for preparing a catalyst for an oxygen reduction reaction comprising the step of thermally decomposing a ground mixture at 800°C or higher and 1100°C or lower.
  6. In paragraph 5, A method for manufacturing a catalyst, wherein the titanium metal-organic framework and the melamine are mixed in a mass ratio of 1:2 to 1:4.
  7. In paragraph 5, A method for preparing a catalyst for an oxygen reduction reaction, wherein the pyrolysis step described above is pyrolysis for 1 to 4 hours.
  8. In paragraph 5, A method for preparing a catalyst for an oxygen reduction reaction, wherein the above titanium metal-organic framework is MIL-125- NH2 .
  9. In paragraph 5, A method for preparing a catalyst for an oxygen reduction reaction, further comprising the step of preparing a titanium metal-organic framework by solvothermally reacting a titanium precursor and an organic ligand.

Description

Catalyst for Oxygen Reduction Reaction and Method for Manufacturing the Same The present invention relates to a catalyst for an oxygen reduction reaction and a method for manufacturing the same. Hydrogen peroxide ( H₂O₂ ) is a substance widely used in various industrial processes , including bleaching and water treatment. The demand for hydrogen peroxide is on the rise, as evidenced by its use as an important disinfectant during the COVID-19 pandemic. Conventionally, hydrogen peroxide was produced using the anthraquinone method, which had the disadvantages of being complex and having high energy consumption. In particular, the production process had a negative impact on the environment, such as generating toxic waste due to the use of hazardous chemicals. Consequently, a method of manufacturing hydrogen peroxide in an eco-friendly manner and with high efficiency through the electrochemical Oxygen Reduction Reaction (ORR) has recently emerged as an alternative. To produce hydrogen peroxide through the oxygen reduction reaction, it is necessary to control the electron transfer pathway using an appropriate electrochemical catalyst. Conventional single-atom precious metal catalysts have faced difficulties in mass-producing hydrogen peroxide due to their high cost and complex manufacturing methods. Therefore, there is a need for research to develop titanium-based electrochemical catalysts that are cost-effective compared to precious metals and can participate in the two-electron ORR reaction under alkaline electrolytes. Figure 1 shows (a) the XRD pattern, (b) the SEM image, (c) the N2 adsorption-desorption isotherm, and (d) the pore size distribution HK plot of the synthesized MIL125- NH2 . Figure 2 shows (a) different SEM images and (b) particle size distribution of the synthesized MIL125- NH2 . Figure 3 shows the XRD patterns of (a) Comparative Example (TiONC-t) and (b) Example (TiONC-MA-t) catalysts according to the pyrolysis temperature. FIG. 4 shows (a) SEM image, (c) TEM image, (e) EDX elemental mapping image of Comparative Example 4 (TiONC-1000), and (b) SEM image, (d) TEM image, and (f) EDX elemental mapping image of Example 4 (TiONC-MA-1000). Figure 5 is an SEM image of (a) Comparative Example 1 (TiONC-700), (b) Comparative Example 2 (TiONC-800), (c) Comparative Example 3 (TiONC-900), and (d) Comparative Example 5 (TiONC-1100). Figure 6 is an SEM image of (a) Example 1 (TiONC-MA-700), (b) Example 2 (TiONC-MA-800), (c) Example 3 (TiONC-MA-900), and (d) Example 5 (TiONC-MA-1100). Figure 7 shows the (a) Ti 2p, (b) O 1s, and (c) N 1s XPS spectra of Example 4 (TiONC-MA-1000) and Comparative Example 4 (TiONC-1000). Figure 8 is a graph summarizing the percentage of the TiN peak area relative to the total area according to the Ti 2p XPS analysis of the catalysts of the example (TiONC-MA-t) and comparative example (TiONC-t), and the ratio of the Ti 3+ peak area relative to the Ti 4+ peak area according to the XPS analysis. Figure 9 is the C 1s XPS spectrum of Example 4 (TiONC-MA-1000) and Comparative Example 4 (TiONC-1000). Figure 10 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Example 1 (TiONC-MA-700). Figure 11 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Example 2 (TiONC-MA-800). Figure 12 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Example 3 (TiONC-MA-900). Figure 13 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Example 5 (TiONC-MA-1100). Figure 14 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Comparative Example 1 (TiONC-700). Figure 15 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Comparative Example 2 (TiONC-800). Figure 16 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Comparative Example 3 (TiONC-900). Figure 17 shows the (a) Ti 2p, (b) O 1s, (c) N 1s, and (d) C 1s XPS spectra of Comparative Example 5 (TiONC-1100). FIG. 18 shows (a) LSV curves and (b) molar selectivity of hydrogen peroxide measured in an RRDE system with the catalyst of Example (TiONC-MA-t), (c) LSV curves and (d) molar selectivity of hydrogen peroxide measured in an RRDE system with the catalyst of Comparative Example (TiONC-t), (e) a graph showing the correlation between the Ti³⁺ / Ti⁴⁺ ratio and molar selectivity of hydrogen peroxide in an RRDE system with the catalyst of Example, and (f) EPR spectra of Example 4 (TiONC-MA-1000), Comparative Example 2 (TiONC-800), and HT- TiO₂ . Figure 19 shows the Tafel slope measured in an RRDE system with (a) the example (TiONC-MA-t) and (b) the comparative example (TiONC-t) catalysts applied. Figure 20 shows the Raman spectra of (a) the comparative example (TiONC-t) and (b) the example (TiONC-MA-t) catalysts. Figure 21 is the FT-IR spectrum of (a) the comparative example (TiONC-t) and (b) the example (TiONC-MA-t) catalysts. Figure 22 shows (a) the XRD spectrum, (b) the Ti 2p XPS spectrum, (c) the O 1s XPS spectrum, (d) the LSV curve wi