4.8 Article

Protons Make Possible Heterolytic Activation of Hydrogen Peroxide over Zr-Based Metal-Organic Frameworks

期刊

ACS CATALYSIS
卷 9, 期 11, 页码 9699-+

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.9b02941

关键词

cyclohexene; epoxidation; heterogeneous catalysis; hydrogen peroxide; metal-organic frameworks; UiO; zirconium

资金

  1. Ministry of Science and Higher Education of the Russian Federation [AAAA-A17-117041710080-4]
  2. Russian Foundation for Basic Research [18-29-04022]
  3. Global Frontier Center for Hybrid Interface Materials (GFHIM)
  4. ISTK [SK-1301]

向作者/读者索取更多资源

The catalytic performance of zirconium-based metal-organic frameworks (UiO-66, UiO-67, and MOF-801) in cyclohexene oxidation with aqueous hydrogen peroxide can be greatly improved by adding a source of protons directly into the reaction mixture. A blend of Zr-MOF and protons favors heterolytic activation of H2O2 and makes possible selective formation of epoxide and diol with negligible formation of allylic oxidation products. Additives of HClO4 suppress the rates of H2O2 decomposition over Zr-MOF and increase oxidant utilization efficiency. No structural changes occur in the acid-activated Zr-MOF. The catalyst does not suffer metal leaching, reveals a truly heterogeneous nature of the catalysis, and can be recovered and reused.

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