In heterogeneous catalysis the local reaction environment around active sites can be tuned to control the reaction activity and selectivity. This can be explored in computational simulations using a prototype chemical reaction on a well-defined crystal surface, through which fundamental understanding of the reaction mechanism under complex reaction environment can be provided. Here we emphasize on aldol condensation of biomass-derived cyclopentanone at the solid-liquid interface. We discuss interfacial reaction engineering of the self- and cross-aldol condensation of biomass-derived ketones over metal-oxide-based catalysts and acid catalysts. In both cases, the reaction kinetics is controlled by the topology of the active sites including the distances between adjacent sites. The role of the water is to bridge the active sites manifested by enhanced rates and shifted rate-determining steps. The phenomena are similar to what we previously reported for metal-catalyzed hydrogenation of furfural in water, but the mechanisms are distinct: in the former hydrogenation reaction, proton shuttling in the water network plays a vital role, while, for aldol condensation between ketones, water-induced remote polarization facilitates the C-C coupling step. This multifaceted role of water provides an additional degree of freedom for manipulating reaction kinetics.

Mechanistic insights into roles of water in aldol condensation of biomass-derived ketones

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