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Cyclohexene oxidation with h 2 o 2 over metal-organic framework mil-125(Ti) : The effect of protons on reactivity. / Maksimchuk, Nataliya; Lee, Ji Sun; Ayupov, Artem et al.
In: Catalysts, Vol. 9, No. 4, 324, 01.04.2019.Research output: Contribution to journal › Article › peer-review
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TY - JOUR
T1 - Cyclohexene oxidation with h 2 o 2 over metal-organic framework mil-125(Ti)
T2 - The effect of protons on reactivity
AU - Maksimchuk, Nataliya
AU - Lee, Ji Sun
AU - Ayupov, Artem
AU - Chang, Jong San
AU - Kholdeeva, Oxana
PY - 2019/4/1
Y1 - 2019/4/1
N2 - The catalytic performance of the titanium-based metal-organic framework MIL-125 was evaluated in the selective oxidation of cyclohexene (CyH) with environmentally friendly oxidants, H 2 O 2 and t BuOOH. The catalytic activity of MIL-125 as well as the oxidant utilization efficiency and selectivity toward epoxide and epoxide-derived products can be greatly improved by acid additives (HClO 4 or CF 3 SO 3 H). In the presence of 1 molar equivalent (relative to Ti) of a proton source, the total selectivity toward CyH epoxide and trans-cyclohexane-1,2-diol reached 75-80% at 38-43% alkene conversion after 45 min of reaction with 1 equivalent of 30% H 2 O 2 at 50 °C. With 50% H 2 O 2 as the oxidant, the total selectivity toward heterolytic oxidation products increased up to 92% at the same level of alkene conversion. N 2 adsorption, powder X-ray diffraction (PXRD), and infrared (IR) spectroscopy studies before and after the catalytic oxidations confirmed the absence of structural changes in the Metal-organic framework (MOF) structure. MIL-125 was stable toward titanium leaching, behaved as a truly heterogeneous catalyst, and could easily be recovered and reused several times without any loss of the catalytic properties.
AB - The catalytic performance of the titanium-based metal-organic framework MIL-125 was evaluated in the selective oxidation of cyclohexene (CyH) with environmentally friendly oxidants, H 2 O 2 and t BuOOH. The catalytic activity of MIL-125 as well as the oxidant utilization efficiency and selectivity toward epoxide and epoxide-derived products can be greatly improved by acid additives (HClO 4 or CF 3 SO 3 H). In the presence of 1 molar equivalent (relative to Ti) of a proton source, the total selectivity toward CyH epoxide and trans-cyclohexane-1,2-diol reached 75-80% at 38-43% alkene conversion after 45 min of reaction with 1 equivalent of 30% H 2 O 2 at 50 °C. With 50% H 2 O 2 as the oxidant, the total selectivity toward heterolytic oxidation products increased up to 92% at the same level of alkene conversion. N 2 adsorption, powder X-ray diffraction (PXRD), and infrared (IR) spectroscopy studies before and after the catalytic oxidations confirmed the absence of structural changes in the Metal-organic framework (MOF) structure. MIL-125 was stable toward titanium leaching, behaved as a truly heterogeneous catalyst, and could easily be recovered and reused several times without any loss of the catalytic properties.
KW - Alkene
KW - Epoxidation
KW - Heterogeneous catalysis
KW - Hydrogen peroxide
KW - Metal-organic framework
KW - MIL-125
KW - Titanium
KW - SELECTIVE OXIDATION
KW - heterogeneous catalysis
KW - titanium
KW - hydrogen peroxide
KW - TITANIUM
KW - EPOXIDATION
KW - metal-organic framework
KW - P-BENZOQUINONES
KW - epoxidation
KW - PHOTOCATALYTIC ACTIVITY
KW - TI
KW - alkene
KW - OLEFINS
KW - HYDROGEN-PEROXIDE
KW - DESULFURIZATION
KW - HETEROGENEOUS CATALYSTS
UR - http://www.scopus.com/inward/record.url?scp=85065395857&partnerID=8YFLogxK
U2 - 10.3390/catal9040324
DO - 10.3390/catal9040324
M3 - Article
AN - SCOPUS:85065395857
VL - 9
JO - Catalysts
JF - Catalysts
SN - 2073-4344
IS - 4
M1 - 324
ER -
ID: 20044070