Sustainable enabling technologies are urgently sought to fulfill 21st century food, energy and material challenges, and to a large extent will be contingent on the design of next-generation catalysts and associated industrial processes. The chemoselective oxidation of unsaturated alcohols is an important reaction class that unlocks the synthesis of diverse chemical intermediates, and will play a pivotal role in efficient biomass valorisation. However, existing heterogeneous catalyst technologies are poorly suited to the chemical transformation of bulky reactants over nanoporous catalysts, and often suffer from low chemoselectivity. New synthetic methodologies are therefore required to engineer novel catalyst architectures and multifunctional catalysts with superior activity, selectivity and lifetime. Here we illustrate new synthetic routes to fabricate mesoporous and hierarchical macroporous-mesoporous frameworks for the selective aerobic oxidation of allylic alcohols and aldehydes, and the benefits of bifunctional metal-metal or metal-base catalysts. Figure 1 (left) illustrates the how interplay between solid base and metal promotes the cascade oxidation of 5-HMF→2,5-FDCA, and important precursor to the biobased polymer PEF. Figure 1 (right) shows how molecular transport between segregated yet communicating catalytically active centres affords a unique and ultraselective route to one-pot oxidations, exemplified for the one-pot cascade oxidation of cinnamyl alcohol→cinnamaldehyde→cinnamic acid over a Pd macroporous-Pt mesoporous/SBA-15 hierarchical silicate in which chemically distinct functionalities are introduced in a spatially orthogonal (mutually exclusive) fashion.

Selective aerobic oxidation of bio-derived molecules over nanostructured catalysts

255th National Meeting (2018)

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