Articles of manufacture and devices and methods of forming and using the same are provided, wherein the article comprises a porous inorganic substrate contained in or bounded by a support made from an inorganic material are provided, wherein said porous substrate and support are heated to a temperature effective to shrink the support onto the porous substrate such that liquid tight contact is formed between the porous substrate and the support. In a preferred aspect, the porous inorganic substrate has a porosity of at least 5%, and is a porous monolith formed using a sol-gel method. The articles thus formed provide a confined fluid flow through the porous substrate, providing superior performance in separations, catalysis, filtration, and the like.