Metal-support interactions in the form of iron-silicate were investigated by an inverse approach, that is, modification of nano-sized iron oxide with surface silicate groups. The presence of surface silicate groups in the calcined catalyst precursor was confirmed using diffuse reflectance infra-red Fourier transform analysis. The genesis of the various iron phases in the presence of surface silicate groups after H-2-activation and the Fischer-Tropsch synthesis was followed. The surface silicate groups are preserved after a hydrogen treatment at 350 degrees C for 16 h, and these surface ligands are associated with the residual iron oxide phase, wilstite. During the Fischer-Tropsch synthesis, alpha-Fe is mostly converted into chi-Fe5C2, whereas FeO is the main source for epsilon-Fe2C. The activity per unit surface area of hexagonal carbide, epsilon-Fe2C, is ca. 25% higher than that of chi-Fe5C2. The presence of surface silicate ligands on epsilon-Fe2C results in a further enhancement of the rate per unit surface area of epsilon-Fe2C by a factor of ca. 3. This is being ascribed to the enhanced availability of hydrogen on the surface due to the presence of the surface silicate groups, which also results in an increase in the methane selectivity, a decrease in the olefin content and a decrease in formation of branched product compounds. (C) 2012 Elsevier Inc. All rights reserved.