Synthesis, Structural Characterization, and Catalytic Performance of a Vanadium-Based Metal-Organic Framework (COMOC-3)

• Published in: European journal of inorganic chemistry Vol. 2012; no. 16; pp. 2819 - 2827
• Main Authors: Liu, Ying-Ya, Leus, Karen, Grzywa, Maciej, Weinberger, David, Strubbe, Katrien, Vrielinck, Henk, Van Deun, Rik, Volkmer, Dirk, Van Speybroeck, Veronique, Van Der Voort, Pascal
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.06.2012; WILEY‐VCH Verlag; Wiley
• Subjects: Chemistry; Chemistry, Inorganic & Nuclear; Heterogeneous ­catalysis; Metal-organic frameworks; Oxidation; Physical Sciences; Science & Technology; Vanadium; Heterogeneous -catalysis; BENZENEDICARBOXYLATE; CONVERSION; MIL-53; Vanadium; Oxidation; Metal-organic frameworks
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201101099

A vanadium 2,6‐naphthalenedicarboxylate, VIII(OH)(O2C–C10H6–CO2)·H2O, denoted as COMOC‐3as (COMOC = Center for Ordered Materials, Organometallics and Catalysis, Ghent University), has been synthesized under hydrothermal conditions by means of both a solvothermal and a microwave synthesis procedure. The structure shows the topology of an aluminium 2,6‐naphthalenedicarboxylate, the so‐called MIL‐69 (MIL = Materials of the Institute Lavoisier). After calcination at 250 °C in air, the VIII center was oxidized to VIV with the structure of VIVO(O2C–C10H6–CO2) (COMOC‐3). The oxidation process was verified by cyclic voltammetry and EPR spectroscopy. The crystallinity was investigated by variable‐temperature XRD. The title compound is stable against air and moisture. The catalytic performance of COMOC‐3 was examined in the liquid‐phase oxidation of cyclohexene. COMOC‐3 exhibited similar catalytic performance to MIL‐47 [VO(O2C–C6H4–CO2)]. The compound is reusable and maintains its catalytic activity through several runs. A vanadium‐based metal–organic framework (COMOC‐3) has been synthesized and fully characterized. It crystallizes in the monoclinic system with the space group C2/c (no. 15). This closed MIL‐69 analogue shows excellent thermal stability and good catalytic performance in the liquid‐phase oxidation of cyclohexene. The catalyst can be regenerated and reused without significant loss of activity.