Provided are methods of preparing an article in which a microporous layer is coated on a temporary carrier substrate and a substrate is then laminated to the microporous layer, prior to removing the temporary carrier substrate from the microporous layer. The microporous layer comprises one or more microporous xerogel layers. Optionally, the microporous layer assembly may comprise one or more non-microporous coating layers which are in contact with at least one of the microporous xerogel layers, and one of the non-microporous coating layers may be coated on the temporary carrier substrate prior to coating the microporous layer. Also provided are articles, such as electrochemical cells, capacitors, fuel cells, ink jet ink printing media, and filtration media, prepared by such methods.