Processes for coating three dimensional inorganic substrates, with shielded surfaces, with transition metal oxide-containing coatings are disclosed. Such processes comprise contacting a substrate with a transition metal oxide precursor, preferably maintaining the precursor coated substrate at conditions to equilibrate the coating, and then oxidizing the precursor to form a substrate containing transition metal oxide on at least a portion of the three dimensions and shielded surfaces of the substrate. Also disclosed are substrates coated with transition metal oxide-containing coatings for use in various applications including catalysis, shielding, heating and electro rheological applications using elements such as inorganic, fluid, porous and polymer matrix elements.