The invention relates to methods of using noble metal-free nickel catalysts to generate a hydrogen-rich gas from gas mixtures containing carbon monoxide and water, such as water-containing syngas mixtures, where the nickel may exist in either a supported or a bulk state. The noble metal-free water gas shift catalyst of the invention comprises Ni in either a supported or a bulk state and at least one of Ge, Cd, In, Sn, Sb, Te, Pb, their oxides and mixtures thereof. The invention is also directed toward noble metal-free nickel catalysts that exhibit both high activity and selectivity to hydrogen generation and carbon monoxide oxidation.