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.

Cu@CuOx/WO3 with photo-regulated singlet oxygen and oxygen adatoms generation for selective photocatalytic aromatic amines to imines.

Photocatalysts can absorb light and activate molecular O2 under mild conditions, but the generation of unsuitable reactive oxygen species often limits their use in synthesizing fine chemicals. To address this issue, we disperse 1 wt% copper on tungsten trioxide (WO3) support to create an efficient catalyst for selective oxidative coupling of aromatic amines to imines under sunlight irradiation at room temperature. Copper consists of a metallic copper core and an oxide shell. Experimental and density functional theory calculations have confirmed that Cu2O is the primary activation site. Under λ < 475 nm, the light excites electrons of the valence bands in Cu2O and WO3, which activate O2 to superoxide radical •O2-. Then rapidly transforms into oxygen adatoms (•O) and oxygen anion radicals (•O-) species on the surface of Cu2O. Simultaneously, it is captured by holes in the WO3 valence band to generate singlet oxygen (1O2). •O bind to 1O2 promoting the coupling reaction of amines. When λ > 475 nm, intense light absorption due to the localized surface plasmon resonance excites numerous electrons in Cu to promote the oxidative coupling with the adsorbed O2. This study presents a promising approach towards the design of high-performance photocatalysts for solar energy conversion and environmentally-friendly oxidative organic synthesis.