Ethyne-Reducing Metal–Organic Frameworks to Control Fabrications of Core/shell Nanoparticles as Catalysts

Abstract

An approach using cobalt metal–organic frameworks (Co–MOF) as precursors is established for the fabrication of cobalt nanoparticles in porous carbon shells (core/shell Co@C). Chemical vapor deposition of ethyne is used for controlling the reduction of cobalt nanoclusters in the MOF and the spontaneous formation of the porous carbon shells. The metallic cobalt cores formed are up to 4–6 nm with the crystal phase varying between hexagonally close-packed (hcp) and face-center-packed (fcc). The porous carbon shells change from amorphous to graphene with the ethyne deposition temperature increasing from 400 to 600 °C. The core/shell Co@C nanoparticles exhibit high catalytic activity in selectively converting syngas (CTY 254.1–312.1 μmolCO gCo–1 s–1) into hydrocarbons (4.0–5.2 gHC g-cat–1 h–1) at 260 °C and 3.0 MPa. In addition to the crystal size and phase, the coordination numbers of the cobalt to oxygen and to other cobalt atoms on the surface of the cobalt nanoparticles and the permeability of the porous ca...