Morphology effect of metal-organic framework HKUST-1 as a catalyst on benzene oxidation

Abstract

An attempt was made to study whether the morphology effect of metal-organic frameworks HKUST-1 could significantly influence the chemical reaction of benzene oxidation. Four representative cupric salts, CuSO₄·5H₂O, Cu(OAc)2·H₂O, CuCl₂·2H₂O and Cu(NO₃)₂·3H₂O, were treated with 1,3,5-benzenetricarboxylic acid under ultrasound or with static method at room temperature to prepare metal-organic frameworks(12 types of HKUST-1 samples). And the as-prepared HKUST-1 materials were comprehensively investigated by X-ray diffraction, scanning electron microscopy and N₂ adsorption-desorption. The HKUST-1 samples with different morphologies and characterisitcs were employed as catalysts for benzene oxidation with H₂O₂ as oxidant at 60 °C in acetonitrile to achieve the aromatic oxygenates and test their yields. In all the HKUST-1 samples, the HKUST-1/SA, HKUST-1/SA0 and HKUST-1/UN had the higher catalytic activities with the yields of benzene oxygenates of 15.9%, 16.6% and 11.7%, respectively, which can be ascribed to the larger pore volume, the stronger benzene adsorption and the smaller fine crystal particles. Comparatively, the HKUST-1/SN0 and HKUST-1/SC0 with more intact crystal, larger surface area, lower pore volume and weaker benzene adsorption had the lower catalytic activities with the yields of benzene oxygenates not more than 4%. Therefore, our results confirmed that employing various cupric precursors to prepare the HKUST-1 samples with different morphologies and characteristics can be considered as a worth strategy to design many more powerful heterogeneous catalysts.

Keywords

HKUST-1 / Metal-organic framework / Morphology effect / Catalytic reaction / Benzene

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