<p>It was found that 1% palladium catalysts supported on nanoglobular carbon (NGC) are quite effective in the hydroamination of furfural with nitrobenzene under mild reaction conditions. The catalytic performance strongly depends on the structure and morphology of NGC support. Among the studied catalysts, the sample based on the NGC, consisting of large carbon nanoglobules and containing highly dispersed palladium nanoparticles, exhibits good activity (78% conversion of furfural) and 83% selectivity to <i>N</i>-furfurylaniline. When studying the effect of reaction conditions, it was shown that an increase in both the reaction temperature and the catalyst-to-furfural ratio leads to an increase in the selectivity to by-products, while the hydrogen pressure has minor effect on the catalytic performance. Moderate temperature and hydrogen pressure (e.g., 90&#xa0;°C and 15 bar H<sub>2</sub>) and low catalyst loading (0.1&#xa0;g of catalyst per 1&#xa0;g of furfural) are favorable to achieve high conversions (no less than 80%) and selectivity (80%). The stability test for one of the Pd/NGC catalysts shows that selectivity to the direction of hydroamination is 96–99% throughout all runs. However, a gradual decline in the activity for the hydrogenation of C = N bond in intermediate imine is observed from run to run, which is apparently due to the poisoning of the active sites by reagents and reaction products. Further directions in the study of Pd/NGC catalysts in the hydroamination of furfural should be aimed at optimizing reaction conditions and also at developing approaches to improving the catalyst stability.</p> Graphical Abstract <p></p>

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Hydroamination of Furfural with Nitrobenzene Over Palladium Catalysts Supported on Nanoglobular Carbon

  • Roman M. Mironenko,
  • Tatyana I. Gulyaeva,
  • Oksana V. Gorbunova,
  • Mikhail V. Trenikhin

摘要

It was found that 1% palladium catalysts supported on nanoglobular carbon (NGC) are quite effective in the hydroamination of furfural with nitrobenzene under mild reaction conditions. The catalytic performance strongly depends on the structure and morphology of NGC support. Among the studied catalysts, the sample based on the NGC, consisting of large carbon nanoglobules and containing highly dispersed palladium nanoparticles, exhibits good activity (78% conversion of furfural) and 83% selectivity to N-furfurylaniline. When studying the effect of reaction conditions, it was shown that an increase in both the reaction temperature and the catalyst-to-furfural ratio leads to an increase in the selectivity to by-products, while the hydrogen pressure has minor effect on the catalytic performance. Moderate temperature and hydrogen pressure (e.g., 90 °C and 15 bar H2) and low catalyst loading (0.1 g of catalyst per 1 g of furfural) are favorable to achieve high conversions (no less than 80%) and selectivity (80%). The stability test for one of the Pd/NGC catalysts shows that selectivity to the direction of hydroamination is 96–99% throughout all runs. However, a gradual decline in the activity for the hydrogenation of C = N bond in intermediate imine is observed from run to run, which is apparently due to the poisoning of the active sites by reagents and reaction products. Further directions in the study of Pd/NGC catalysts in the hydroamination of furfural should be aimed at optimizing reaction conditions and also at developing approaches to improving the catalyst stability.

Graphical Abstract