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 Cu(0) 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 Cu(0) and Cu(+) active species, confinement effects, an intrinsically high surface area of Cu(0) and Cu(+) and a unique tunable tubular morphology, has potential applications in high-temperature hydrogenation reactions.