Single-site catalyst promoters accelerate metal-catalyzed nitroarene hydrogenation

Atomically dispersed supported metal catalysts are drawing wide attention because of the opportunities they offer for new catalytic properties combined with efficient use of the metals. We extend this class of materials to catalysts that incorporate atomically dispersed metal atoms as promoters. The catalysts are used for the challenging nitroarene hydrogenation and found to have both high activity and selectivity. The promoters are single-site Sn on TiO2 supports that incorporate metal nanoparticle catalysts. Represented as M/Sn-TiO2 (M = Au, Ru, Pt, Ni), these catalysts decidedly outperform the unpromoted supported metals, even for hydrogenation of nitroarenes substituted with various reducible groups. The high activity and selectivity of these catalysts result from the creation of oxygen vacancies on the TiO2 surface by single-site Sn, which leads to efficient, selective activation of the nitro group coupled with a reaction involving hydrogen atoms activated on metal nanoparticles. Understanding of the structures and roles of catalyst promoters markedly lags behind the understanding of the structures and roles of catalytic sites. Here, the authors address this challenge by incorporating a single-site promoter—tin—on a TiO2 surface to enhance the catalytic activity of various metals on the TiO2 in selective hydrogenation of nitroarenes.