The invention is directed toward methods of using alkali-containing catalysts for generation of hydrogen-rich gas at temperatures of less than about 260° C. A WGS catalyst of the invention may have the following composition: a) at least one of Pt, Ru, their oxides and mixtures thereof; b) Na, its oxides or mixtures thereof; and optionally, c) Li, its oxides and mixtures thereof. The catalysts may be supported on a variety of catalyst support materials. The invention is also directed toward catalysts that exhibit both high activity and selectivity to hydrogen generation and carbon monoxide oxidation.