Geminal-atom catalysis for cross-coupling.

Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis. However, the architecture of these mononuclear metal species stabilized on solid supports may not be optimal for catalysing complex molecular transformations owing to restricted spatial environment and electronic quantum states. Here we report a class of heterogeneous geminal-atom catalysts (GACs), which pair single-atom sites in specific coordination and spatial proximity.

Graphitic phosphorus coordinated single Fe atoms for hydrogenative transformations.

Single-atom metal-nitrogen-carbon (M-N-C) catalysts have sparked intensive interests, however, the development of an atomically dispersed metal-phosphorus-carbon (M-P-C) catalyst has not been achieved, although molecular metal-phosphine complexes have found tremendous applications in homogeneous catalysis. Herein, we successfully construct graphitic phosphorus species coordinated single-atom Fe on P-doped carbon, which display outstanding catalytic performance and reaction generality in the heterogeneous hydrogenation of N-heterocycles, functionalized nitroarenes, and reductive amination reactions, while the corresponding atomically dispersed Fe atoms embedded on N-doped carbon are almost inactive under the same reaction conditions. Furthermore, we find that the catalytic activity of graphitic phosphorus coordinated single-atom Fe sharply decreased when Fe atoms were transformed to Fe clusters/nanoparticles by post-impregnation Fe species.

Conversion of cellulose into isosorbide over bifunctional ruthenium nanoparticles supported on niobium phosphate.

Considerable effort has been applied to the development of new processes and catalysts for cellulose conversion to valuable platform chemicals. Isosorbide is among the most interesting products as it can be applied as a monomer and building block for the future replacement of fossil resource-based products. A sustainable method of isosorbide production from cellulose is presented in this work.