Towards the selectivity distinction of phenol hydrogenation on noble metal catalysts

Abstract

Selective hydrogenation of phenol to cyclohexanone is intriguing in chemical industry. Though a few catalysts with promising performances have been developed in recent years, the basic principle for catalyst design is still missing owing to the unclear catalytic mechanism. This work tries to unravel the mechanism of phenol hydrogenation and the reasons causing the selectivity discrepancy on noble metal catalysts under mild conditions. Results show that different reaction pathways always firstly converge to the formation of cyclohexanone under mild conditions. The selectivity discrepancy mainly depends on the activity for cyclohexanone sequential hydrogenation, in which two factors are found to be responsible, i.e. the hydrogenation energy barrier and the competitive chemisorption between phenol and cyclohexanone, if the specific co-catalyzing effect of H2O on Ru is not considered. Based on the above results, a quantitative descriptor, Eb(one/pl)/Ea, in which Ea can be further correlated to the d band center of the noble metal catalyst, is proposed by the first time to roughly evaluate and predict the selectivity to cyclohexanone for catalyst screening.

Keywords

• Phenol
• Selective hydrogenation
• Cyclohexanone
• DFT
• Noble metal catalysts