High-Efficiency Solar Transformation of Sugars via a Heterogenous Gallium(III) Catalyst.

Extremely limited research exploring the photocatalytic potential of main group metals, such as aluminum, gallium, and tin, has been undertaken due to their weak light harvesting properties. This study reports the efficient transformation of sugars to 5-hydroxymethylfurfural (HMF) with high yield employing an original heterogeneous photocatalyst comprising a gallium(III) complex immobilized on an alumina support. Under visible light irradiation, the reaction rate of HMF formation is ~143 times higher than the equivalent thermal reaction performed in the absence of light. The turnover number (TON) of the heterogeneous gallium(III) photocatalyst was as high as 1500, which was ca. two orders of magnitude higher than the TON of the homogeneous gallium(III) system. It is proposed that photoirradiation significantly enhances the Lewis acidity of the catalyst by forming a semi-coordination state between gallium(III) and N-donor ligands, enabling the increased interaction of reactant sugar molecules with gallium(III) active sites. Consistent with this, the photoresponsive coordination of the gallium(III) complex and the abstraction of the hydroxy group by the metal under irradiation with visible light is observed by NMR spectroscopy for the first time. These findings demonstrate that efficient photocatalysts derived from the main group elements can facilitate biomass conversion using visible light.