Journal
CATALYSIS TODAY
Volume 213, Issue -, Pages 93-100Publisher
ELSEVIER
DOI: 10.1016/j.cattod.2013.03.037
Keywords
Iridium; Nitrobenzene; Hydrogenation; Heterogeneous catalyst
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This study is based on 1%Ir/ZrO2 catalyst which was studied in the hydrogenation of aromatic meta-substituted nitrobenzene in liquid phase. The catalyst was prepared by traditional impregnation method using IrCl3 and it has been characterized in terms of temperature-programmed reduction (TPR), ICP-MS, BET area, X-ray diffraction, HR-TEM and XPS measurements. The hydrogenation was evaluated in a batch type reactor at 298 K using ethanol like a solvent. The catalyst showed the formation of zero valent and partially oxidized Iridium (Ir delta+) is established post-TPR and XPS characterization. The metal particle size exhibited a wide distribution with mean size 1.8 nm. Ir/ZrO2 was active in all the hydrogenation reactions with elevated conversion and promoted exclusive NO2 group reduction, resulting in the sole formation of the corresponding amino-compound except for -CHO and -CH=CH2 meta-substituted nitrobenzene. We associate this response to a reducible group competition between -NO2 and -CHO or -CH=CH2. Reactant activation on the catalyst generates a negatively charged intermediate, consistent with a nucleophilic mechanism. The presence of electron-donating substituents is shown to decrease -NO2 reduction rate. This effect is quantified in terms of the Hammett relationship where a linear correlation between the substituent constant (sigma(i)) and rate is established and a reaction constant (rho) 0.639. The data generated provide the first report of the catalytic action of supported Ir in the hydrogenation of meta-substituted nitroarenes and establish the nature of the hydrogenation en liquid phase. (C) 2013 Elsevier B. V. All rights reserved.
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