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With the decline of petroleum reserves and the increase in social concern over environmental problems, the conversion of biomass into value-added chemicals and fuel has recently drawn worldwide attention. Hydrogenation and hydrogenolysis are two reactions very often present in biorefinering of lignocellulose-based feeds. Generally, hydrogenation is applied to the saturation of the CC and/or CO bonds in the biomass platform molecules. Hydrogenolysis is a reaction in which a carbon–carbon or carbon–heteroatom single bond is cleaved by the addition of hydrogen atoms. This chapter focuses on various mechanistic features of hydrogenation and hydrogenolysis applied to the conversion of biogenic feeds. The chapter presents some of the relevant case studies, not only assessing the current state-of-the-art in the field but also highlighting the recent insights towards the rational catalyst design for lignocellulose valorization.

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