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This review deals with “classical” porous glasses which are prepared by physical phase separation of alkali borosilicate glasses of suitable composition in combination with selective leaching. The resulting materials are characterized by a controllable pore size in the nanometer range, high mechanical, thermal and chemical stability and an adjustable macroscopic shape, which enables manufacturing of glass monoliths with various geometries. As a result of their formation, porous glasses obtained from physical phase separation exhibit a monomodal pore structure. There are only a few examples in the literature for the synthesis of hierarchically porous glasses. This review covers several synthesis strategies for the introduction of hierarchy into “classical” porous glass monoliths, including sintering and fusion of alkali borosilicate initial glasses as well as partial or complete pseudomorphic transformation of porous glasses into zeolites or ordered mesoporous materials.
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