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Catalytic Performance of Zr-Based Metal–Organic Frameworks Zr-abtc and MIP-200 in Selective Oxidations with H2O2. / Maksimchuk, Nataliya V.; Ivanchikova, Irina D.; Cho, Kyung Ho и др.
в: Chemistry - A European Journal, Том 27, № 23, 21.04.2021, стр. 6985-6992.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Catalytic Performance of Zr-Based Metal–Organic Frameworks Zr-abtc and MIP-200 in Selective Oxidations with H2O2
AU - Maksimchuk, Nataliya V.
AU - Ivanchikova, Irina D.
AU - Cho, Kyung Ho
AU - Zalomaeva, Olga V.
AU - Evtushok, Vasiliy Yu
AU - Larionov, Kirill P.
AU - Glazneva, Tatiana S.
AU - Chang, Jong San
AU - Kholdeeva, Oxana A.
N1 - Publisher Copyright: © 2021 Wiley-VCH GmbH
PY - 2021/4/21
Y1 - 2021/4/21
N2 - The catalytic performance of Zr-abtc and MIP-200 metal–organic frameworks consisting of 8-connected Zr6 clusters and tetratopic linkers was investigated in H2O2-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 H2O2 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 H2O2-based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2O2.
AB - The catalytic performance of Zr-abtc and MIP-200 metal–organic frameworks consisting of 8-connected Zr6 clusters and tetratopic linkers was investigated in H2O2-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 H2O2 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 H2O2-based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2O2.
KW - alpha,beta-unsaturated ketones
KW - epoxidation
KW - hydrogen peroxide
KW - metal–organic frameworks
KW - Zr
UR - http://www.scopus.com/inward/record.url?scp=85100933240&partnerID=8YFLogxK
U2 - 10.1002/chem.202005152
DO - 10.1002/chem.202005152
M3 - Article
C2 - 33559238
AN - SCOPUS:85100933240
VL - 27
SP - 6985
EP - 6992
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
SN - 0947-6539
IS - 23
ER -
ID: 28072691