CO2 hydrogenation to short-chain hydrocarbons was investigated over iron catalysts supported on oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (CNTs) and on silica, which were synthesized by the dry impregnation method using ammonium ferric citrate as precursor. The reduction of the calcined catalysts was examined in detail using temperature-programmed reduction in H-2 and in situ X-ray absorption near-edge structure (XANES) analysis. The XANES results revealed that the mixture of hematite and magnetite was gradually transformed into wustite and metallic iron during heating in H-2. Iron oxide nanoparticles supported on nitrogen-functionalized CNTs were easier to reduce compared to those on oxygen-functionalized CNTs indicating a promoting effect of the nitrogen functional groups. The interaction between iron oxide and silica was found to be much stronger inhibiting the reduction to metallic iron. As a result, the catalytic activity of iron nanoparticles supported on CNTs in CO2 hydrogenation at 360 degrees C, 25 bar and a H-2:CO2 ratio of 3 was almost twofold higher compared with iron supported on silica. CO2 was converted into C-1-C-5 hydrocarbons with CO and methane as major products over all catalysts. The Fe/NCNT catalyst achieved the highest olefin selectivity of 11% in the hydrocarbons range of C-2-C-5. In contrast, mostly paraffins were formed over the Fe/SiO2 catalyst. (C) 2014 Elsevier B.V. All rights reserved.