Doping Pt/ceria catalysts with the Group 1 alkali metals was found to lead to an important weakening of the C-H bond of formate and methoxy species. This was demonstrated by a shift to lower wavenumbers of the formate and methoxy ν(CH) vibrational modes by DRIFTS spectroscopy. Li and Na-doped Pt/ceria catalysts were tested relative to the undoped catalyst for low temperature water-gas shift and methanol steam reforming using a fixed bed reactor and exhibited higher catalytic activity. Steaming of formate and methoxy species pre-adsorbed on the catalyst surface during in-situ DRIFTS spectroscopy suggested that the species were more reactive for dehydrogenation steps in the catalytic cycle for the Li and Na-doped catalysts relative to undoped Pt/ceria. However, with increasing atomic number over the series of alkali-doped catalysts, the stability of a fraction of the carbonate species was found to increase. This was observed during TPD-MS measurements of the adsorbed CO 2 probe molecule by a systematic increase of a high temperature peak for a fraction of the CO2 desorbed. This result indicates that alkali-doping is an optimization problem-that is, while improving the dehydrogenation rates of methoxy and formate species, the carbonate intermediate stability increases, making it difficult to liberate the CO2. Infrared spectroscopy results of CO adsorbed on Pt and ceria suggest that the alkali dopant is located on, and electronically modifies, both the Pt and ceria components. The results not only lend further support to the role that methoxy and formate species play as intermediates in the catalytic mechanisms, but also provide a path forward for improving rates by means other than resorting to higher noble metal loadings. © 2007 Springer Science+Business Media, LLC.