We report on the preparation and application of novel heterogeneous supported ruthenium catalysts. The catalysts are active in the synthesis of formic acid from the hydrogenation of carbon dioxide and are characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction analysis and transmission electron microscopy. Abundant hydroxyl groups, which interact with the ruthenium components, play an important role in the catalytic reactions. Highly dispersed ruthenium hydroxide species enhance the hydrogenation of CO2, while crystalline RuO2 species, which are formed from the relatively high ruthenium content or the pH of the solution during preparation of the catalyst, restrict the production of formic acid. Optimal activity of ruthenium hydroxide as a catalyst for the hydrogenation of CO2 to formic acid is achieved over a gamma-Al2O3 supported 2.0 wt% ruthenium catalyst, which is prepared in a solution of pH 12.8 with NH3 center dot H2O as a titration solvent. A possible hydrogenation mechanism for the hydroxide ruthenium catalyst is proposed. (C) 2010 Elsevier B.V. All rights reserved.