Direct Alkylation of Benzenes With Simple Alkanes Promoted by Solid Acids and Supported Pt Nanoparticles Combined System

ABSTRACT The direct alkylation of benzene with alkanes is a challenging transformation because it requires selective C–C bond formation from inert C–H bonds while suppressing cracking. Here, we demonstrate that a physical mixture of supported Pt nanoparticles and solid acids efficiently catalyzes the direct alkylation of benzenes with alkanes at 150°C. Pt nanoparticles supported on hydrotalcite (Pt/HT) promote recombination of atomic hydrogen to molecular hydrogen, while the alkane is activated on solid acid surface to react with benzene giving alkylbenzene and atomic hydrogen which migrates to the Pt nanoparticles via reverse hydrogen spillover. Among the solid acids examined, H‐mordenite exhibit high activity and selectivity toward mono‐alkylated benzene products, with selectivity up to 99% for heptylbenzene. Catalyst separation experiments verify that close proximity of the supported Pt nanoparticles and acid components is essential for catalytic activity, consistent with an interparticle hydrogen spillover mechanism. The catalytic performance depends strongly on the structure of the solid acid, governing both conversion and product distribution. These results establish hydrogen‐spillover‐mediated metal–acid cooperation as an effective strategy for direct benzene–alkane alkylation.