A copper-phyllosilicate core-sheath nanoreactor for carbon–oxygen hydrogenolysis reactions

Hydrogenolysis of carbon–oxygen bonds is a versatile synthetic tool in organic synthesis. Copper-based catalysts have been intensively explored as the copper sites account for the highly selective hydrogenation of carbon–oxygen bonds. However, the inherent drawback of conventional copper-based catalysts is the deactivation by metal-particle growth and unstable surface Cu0 and Cu+ active species in the strongly reducing hydrogen and oxidizing carbon–oxygen atmosphere. Here we report the superior reactivity of a core (copper)-sheath (copper phyllosilicate) nanoreactor for carbon–oxygen hydrogenolysis of dimethyl oxalate with high efficiency (an ethanol yield of 91%) and steady performance (>300 h at 553 K). This nanoreactor, which possesses balanced and stable Cu0 and Cu+ active species, confinement effects, an intrinsically high surface area of Cu0 and Cu+ and a unique tunable tubular morphology, has potential applications in high-temperature hydrogenation reactions. Nanoscale copper catalysts are useful for the selective hydrogenation of carbon–oxygen bonds, although they may be deactivated under harsh conditions. Here the authors report the enhanced activity and stability of core-sheath copper-phyllosilicate nanoreactors due to electronic and morphological effects.