Technologies for
the processing of lignocellulosic biomass into
fuels and chemicals are generally focused on selective chemical transformation
of the three different types of constituents: cellulose, hemicellulose
and lignin. In this regard, heterogeneous catalytic reactions are
employed to defunctionalize and upgrade the platform molecules obtained
selectively from these constituents. Herein, a selection of studies
are discussed which are adapted to deoxygenate and valorize the biomass-derived
platform molecules with a specific focus on understanding the reaction
mechanisms and rational design of a heterogeneous catalyst. The selection
of the deoxygenation process constituted a combination of two or three
reactions. For example, ring-opening reactions of the cyclic compounds
are studied with decarboxylation, dehydration, hydrogenation and/or
Diels–Alder reaction carried out on metal, acid and/or oxide
catalysts. The platform molecules studied here include an array of
saturated lactones, 2-pyrones, cyclic ethers, furans and phenolic
compounds. In the study of lactones, mechanistic insights are provided
to understand the selectivity trend over the Brønsted and Lewis
acid catalysts for ring-opening and decarboxylation reactions leading
to the formation of α-olefins. For 2-pyrones, the integrated
bio- and chemo-catalytic process is studied in which a 2-pyrone molecule
obtained from fermentation media may undergo Diels–Alder, hydrogenation
combined with ring-opening, decarboxylation and dehydration reactions
to yield the target product. Ring-opening studies on cyclic ethers,
including furanic compounds, are focused on mechanistic observations
in the C–O hydrogenolysis reaction, leading to the design of
bimetallic alloys to produce terminal diols and carboxylic acids.
In extension to this, rational thoughts on the design of bimetallic
catalysts are elucidated in the hydrodeoxygenation of the phenolic
compounds.