Efficient molybdenum(vi) modified Zr-MOF catalysts for epoxidation of olefins

Abstract

Efficient molybdenum(VI) modified Zr-MOF catalysts have been successfully prepared for the epoxidation of olefins. The stable and porous Zr-MOF (UiO-66(NH 2 )) was modified with salicylaldehyde, pyridine-2aldehyde, or 2-pyridine chloride by the post-synthesis modification (PSM) method, and then the Mobased catalyst was loaded by a chelating method. The MOFs not only act as the carriers of the Mo(VI) catalyst, but also improve the contacting ability between the substrate and the active center of the Mo(VI) compound. The high dispersion of the Mo catalyst on Zr-MOF and the big pore size of MOF guarantee sufficient contact between substrate and catalytic active center, thus accelerating the rate of reaction and providing improved catalytic efficiency for the epoxidation of olefins. The obtained Zr-MOF catalyst exhibited high activity for the epoxidation of olefins with 70 wt% tert-butyl hydroperoxide (TBHP) or 30% H 2 O 2 as the oxygen sources. Furthermore, MoO 2 (acac) 2 loaded Zr-MOF was prepared in the same way, and it also showed good catalytic performance for the epoxidation of olefins.

Synthesis of UiO-66-NH2 derived heterogeneous copper (II) catalyst and study of its application in the selective aerobic oxidation of alcohols

“…Initially, the porous UiO-66-NH 2 was synthesized by previous reported work with ZrCl 4 and NH 2 -BDC in DMF [35,36]. Then, the free amino groups were modified with salicylaldehyde to fabricate the UiO-66-Sal.…”

“…The UiO-66-NH 2 crystals were prepared according to the literature procedure [35][36][37]. The prepared UiO-66-NH 2 (1 g) was dispersed in 30 mL acetonitrile in a round-bottomed flask and stirred for 30 min.…”

Amino‐Induced 2D Cu‐Based Metal–Organic Framework as an Efficient Heterogeneous Catalyst for Aerobic Oxidation of Olefins

“…[62] So far,t he PSMets trategy mainly focuseso nt he performance regulation of 3D MOFs. [63] The PSMet of 2D MOFs has only been reported in rare cases because the organic frameworks of the reported 2D MOFs usually have no extra functional groups that can be modified, [64,65] thusmaking it less feasible to anchormetal catalyst by PSMet. Here, we report the preparation of the 2D MOFsupported Pd single-site heterogeneous catalystC u-AIA-PC-Pd by employing Cu-AIA as a2 DMOF support.…”

Recent Advances in Facile Liquid Phase Epoxidation of Light Olefins over Heterogeneous Molybdenum Catalysts

“…The introduction of a second metal cation often shows synergistic performances. For example, Tang et al . successfully prepared stable and porous Mo modified Zr‐MOF catalysts.…”

“…[131] The introduction of a second metal cation often shows synergistic performances. For example, Tang et al [132] [133] present the post-modification of a gallium-based MOF, denoted as COMOC-4, with a Mo-complex. The Mo@COMOC-4 was evaluated as a catalyst in the epoxidation of cyclohexene (Y = 81 %), cyclooctene (Y = 68 %) and cyclododecene (Y = 42 %) employing TBHP in decane as oxidant at 50°C (Table S6, Table S6, #20) was tested for the epoxidation of cyclohexene and compared to a zirconia-supported analogue Mo-ZrO 2 (Y = 96 %, Table S6, #21) catalysts.…”