Abstract:
|
Selective conversion of biomass-derived substrates in
heterogeneous catalysis can be achieved through the functionalization of
nanoparticles with surface modifiers (ligands). However, full understanding
of reaction mechanisms at the atomic level of detail is still
limited. Herein we rely on computational approaches to address this
challenge. We employ Density Functional Theory to understand the
role of phosphine-decorated palladium nanoparticles in the decarbonylation
of fatty acids to produce linear α-olefins. While self-assembled
monolayers of monodentate ligands completely passivate the metal
surface, the flexibility of bidentate counterparts allows the creation of
transient cavities that: (i) enhance selectivity and (ii) prevent catalyst
deactivation. Such detailed insight provided by theory can pave the way
for a rational design of metal−ligand interfaces in biomass upgrading. |