This paper reports, for the first time, complete arene hydrogenation of phenolic compounds as lignin monomers over a non-noble metal catalyst supported by a general material. A type of nano-sized Ni catalyst was prepared in ethanol and in situ supported by ZSM-5 zeolite through general borohydride reduction of Ni2+ to Ni0, but with application of a simple ligand, pyridine. This catalyst showed an activity so high as to completely or near completely hydrogenate the aromatic rings of phenol and its twelve derivatives as potential lignin monomers at 180 °C. The activity was clearly higher than that of another type of conventional Ni catalyst prepared in the absence of pyridine. Analyses of the catalysts by TEM/EDS, XPS, XAFS and others demonstrated that pyridine had crucial roles in selective formation of nano-sized Ni and maintenance of its activity by appropriate interaction with the support. This paper also shows our theoretical approach to the mechanism of the borohydride reduction. First-principles calculations based on density functional theory (DFT) revealed the reaction pathway from Ni2+ to Ni0 and the role of pyridine, which was validated by some experimental facts. The DFT calculations also explain the variety of reactivities of the lignin monomers, which are strongly influenced by their molecular electrostatic and steric nature.
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)