Performance of a NiFe₂O₄@Co Core-Shell Fischer-Tropsch Catalyst: Effect of Low Temperature Reduction

In situ TEM gas-cell imaging and spectroscopy with in situ XRD have been applied to reveal morphological changes in NiFe₂O₄@Co₃O₄ core-shell nanoparticles in hydrogen. The core-shell structure is retained upon reduction under mild conditions (180 °C for 1 h), resulting in a partially reduced shell. The core-shell structure was retained after exposing these reduced NiFe₂O₄@Co₃O₄ core-shell nanoparticles to Fischer-Tropsch conditions at 230 °C and 20 bar. Slightly harsher reduction (230 °C, 2 h) resulted in restructuring of the NiFe₂O₄@Co₃O₄ core-shell nanoparticles to form cobalt islands in addition to partially reduced NiFe₂O₄. NiFe₂O₄ underwent further transformation upon exposure to Fischer-Tropsch conditions, resulting in the formation of iron carbide and nickel/iron-nickel alloy. The turnover frequency in the Fischer-Tropsch synthesis over NiFe₂O₄@Co₃O₄ core-shell nanoparticles reduced in hydrogen at 180 °C for 1 h was estimated to be less than 0.02 s^-1 (cobalt-time yield of 8.40 μmol^.g^-1.s^-1) with a C₅₊ selectivity of 38 C-%. The low turnover frequency under these conditions in relation to the turnover frequency obtained with unsupported cobalt is attributed to the strain in the catalytically active cobalt.