Catalytic Performance of Zr‐Based Metal–Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H 2 O 2
| Autor: | Jong-San Chang, Kirill P. Larionov, Nataliya V. Maksimchuk, Tatiana S. Glazneva, Vasiliy Yu. Evtushok, Irina D. Ivanchikova, Olga V. Zalomaeva, Kyung Ho Cho, Oxana A. Kholdeeva |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
010405 organic chemistry
Organic Chemistry Substrate (chemistry) General Chemistry 010402 general chemistry 01 natural sciences Combinatorial chemistry Catalysis 0104 chemical sciences Sulfone chemistry.chemical_compound Thioether chemistry Nucleophile Electrophile Metal-organic framework Selectivity |
| Zdroj: | Chemistry – A European Journal. 27:6985-6992 |
| ISSN: | 1521-3765 0947-6539 |
| DOI: | 10.1002/chem.202005152 |
| Popis: | The catalytic performance of Zr-abtc and MIP-200 metal-organic frameworks consisting of 8-connected Zr6 clusters and tetratopic linkers was investigated in H2 O2 -based selective oxidations and compared with that of 12-coordinated UiO-66 and UiO-67. Zr-abtc demonstrated advantages in both substrate conversion and product selectivity for epoxidation of electron-deficient C=C bonds in α,β-unsaturated ketones. The significant predominance of 1,2-epoxide in carvone epoxidation, coupled with high sulfone selectivity in thioether oxidation, points to a nucleophilic oxidation mechanism over Zr-abtc. The superior catalytic performance in the epoxidation of unsaturated ketones correlates with a larger amount of weak basic sites in Zr-abtc. Electrophilic activation of H2 O2 can also be realized, as evidenced by the high activity of Zr-abtc in epoxidation of the electron-rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr-abtc structure after the catalysis. The low activity of MIP-200 in H2 O2 -based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2 O2 . |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|