Deoxydehydration of Biomass-Derived Polyols Over Silver-Modified Ceria-Supported Rhenium Catalyst with Molecular Hydrogen

Olefin production from polyols via deoxydehydration (DODH) was carried out over Ag-modified CeO₂-supported heterogeneous Re catalysts with H₂ as a reducing agent. Both high DODH activity and low hydrogenation ability for C=C bonds were observed in the reaction of erythritol, giving a 1,3-butadiene yield of up to 90 % under “solvent-free” conditions. This catalyst is applicable to other substrates such as methyl glycosides (methyl α-fucopyranoside: 91 % yield of DODH product; methyl β-ribofuranoside: 88 % yield), which were difficult to be converted to the DODH products over the DODH catalysts reported previously. ReO_x-Ag/CeO₂ was reused 3 times without a decrease of activity or selectivity after calcination as regeneration. Although the transmission electron microscopy energy-dispersive X-ray spectroscopy and X-ray absorption fine structure analyses showed that Re species were highly dispersed and Ag was present as metal particles with various sizes from well-dispersed species (<1 nm) to around 5 nm particles, the catalysts prepared from size-controlled Ag nanoparticles showed similar performance, indicating that the catalytic performance is insensitive to the Ag particle size.