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). Ethyne deposition 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-closepacked (hcp) and face-centre-packed (fcc). The porous carbon shells changes from amorphous to graphene with the ethyne deposition temperature increasing from 400 to 600 o C. The core/shell Co@C nanoparticles exhibit high catalytic activity in selectively converting syngas (CTY: 254.1-312.1 μmolCOꞏgCo-1 ꞏs-1) into hydrocarbons (4.0-5.2 gHCꞏg-cat-1 ꞏh-1) at 260 o C. As well as 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 carbon shell have been related to the catalytic performance in FTS reactions.

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A new kinetic model of the Fischer-Tropsch synthesis (FTS) is proposed to describe the non-Anderson-Schulz-Flory (ASF) product distribution. The model is based on the double-polymerization monomers hypothesis, in which the surface C 2 * species acts as a chain-growth monomer in the lightproduct range, while C 1 * species acts as a chain-growth monomer in the heavy-product range. The detailed kinetic model in the Langmuir-Hinshelwood-Hougen-Watson type based on the elementary reactions is derived for FTS and the water-gas-shift reaction. Kinetic model candidates are evaluated by minimization of multiresponse objective functions with a genetic algorithm approach. The model of hydrocarbon product distribution is consistent with experimental data (