Article ID Journal Published Year Pages File Type
61998 Journal of Catalysis 2010 9 Pages PDF
Abstract

The hydrogenation of chloronitrobenzene to chloroaniline was investigated over Ni/TiO2 at 35 °C in supercritical CO2 (scCO2), ethanol, and n-hexane. The reaction rate followed the order of scCO2 > n-hexane > ethanol. In scCO2, the selectivity to chloroaniline and to aniline over Ni/TiO2 were 97–99.5% and <1%, respectively, in the conversion range of 9–100%. The high chemoselectivity to chloroaniline cannot be achieved over Ni/TiO2 in ethanol and n-hexane. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions of CO2 with the following reactant and reaction intermediates: chloronitrobenzene, chloronitrosobenzene, and N-chlorophenylhydroxylamine. The molecular interaction modifies the reactivity of each species and accordingly the reaction rate and the selectivity. The influence of Cl substituent on the interaction modes of CO2 with these reacting species is discussed. Possible reaction pathways for the hydrogenation of chloronitrobenzene in scCO2 over Ni/TiO2 are also proposed.

Graphical abstractThe chemoselective hydrogenation of chloronitrobenzene to chloroaniline can be achieved at any conversion levels up to 100% over Ni/TiO2 in scCO2 at 35 °C.Figure optionsDownload full-size imageDownload high-quality image (51 K)Download as PowerPoint slide

Related Topics
Physical Sciences and Engineering Chemical Engineering Catalysis
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