The invention provides active, affordable, durable, and sulfur-tolerant catalysts and related precursors and processes useful in hydrogen production. The catalysts have a wide applicability. For example, in one embodiment, the invention provides sulfur-tolerant catalysts which, when used in a catalytic fuel processor, will facilitate sufficient hydrogen generation within 30 seconds or so of automobile start-up to generate around 50 kW of fuel cell power. Catalysts of the instant invention are made by reducing a catalyst precursor comprising a support phase impregnated with one or more elemental transition metals, wherein: (a) the support phase is formed by dispersion of a monolayer on the surface of a high surface area alumina support; and (b) the monolayer comprises XOnYO2, where (1) XOn is a redox active metal oxide and n is either 1.5, 2, or 2.5 depending on the oxidation number of X, and (2) YO2 is a redox inactive metal oxide. Ni—V2O5—ZrO2/Al2O3 catalysts of the instant invention are preferred.