DOI: 10.1002/adfm.200500280 Recent Advances in the Design of Polymerizable Lyotropic Liquid-Crystal Assemblies for Heterogeneous Catalysis and Selective Separations** By Douglas L. Gin,* Xiaoyun Lu, Parag R. Nemade, Cory S. Pecinovsky , Yanjie Xu, and Meijuan Zhou 1. Introduction Solid-state materials with well-defined, periodic pores on the nanometer and sub-nanometer scales play important roles in materials science, especially in the areas of heterogeneous ca- talysis and separations. The most prevalent of these materials are inorganic zeolites, which are crystalline, open-framework aluminosilicate structures with uniform, interconnected pores in the 0.3–1.0 nm range. [1] Zeolites are widely used in industry as molecular-shape- and -size-selective catalysts that allow fa- cile isolation and recovery because of their solid-state nature. [2] They are able to accelerate reactions by localizing reactants in their pores and by providing a high local concentration of ac- tive sites (typically acidic or basic sites). They are also able to achieve high selectivity in many reactions because the nano- pores impose dimensional constraints. Reactant molecules with certain sizes or shapes can enter these nanopores more easily than other reactants, and the formation of certain transition- state configurations can also be favored over others. [2] In addi- tion to heterogeneous catalysis, zeolites have been utilized for separation applications because of their molecular-size- and - shape-selective properties. Zeolites are commonly used as se- lective solid sorbents, thereby earning them the alternative de- scriptor, “molecular sieves”. [3] More recently, zeolites have been successfully fabricated into supported and composite films to serve as membranes for use in highly selective flow- based separations of small molecules such as light gases (e.g., O 2 /N 2 separations). [4] Although zeolites have many advantages, they also have some inherent limitations. For example, they are brittle, intractable solids that not amenable to processing or fabrication into forms such as continuous films or fibers. [1] This is why the preparation of viable zeolite membranes has been difficult until recently. Although there has been a great deal of Adv. Funct. Mater. 2006, 16, 865–878 © 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 865 Organic lyotropic liquid-crystal (LLC) assemblies mimic molecular sieves in their nanoporous structures and their ability to incorporate catalytic functional groups. This article focuses on recent advances made by our research group in incorporating new catalytic properties into polymerizable LLC assemblies and studying the molecular- transport properties of the crosslinked networks. – [*] Prof. D. L. Gin, C. S. Pecinovsky Department of Chemistry and Biochemistry University of Colorado Boulder, CO 80309 (USA) E-mail: gin@spot.colorado.edu Prof. D. L. Gin, X. Lu, P. R. Nemade, Y. Xu, M. Zhou Department of Chemical and Biological Engineering University of Colorado Boulder, CO 80309 (USA) [**] Financial support for this research from the following agencies is gratefully acknowledged: The Office of Naval Research (N00014-02- 1-0383 and N00014-03-1-0993); the National Science Foundation (DMR-0111193); the NSF Liquid Crystal Materials Research Center at CU Boulder (DMR-0213918); and the U.S. Army Research Office (DAAD19-02-C-0065) and the U.S Dept. of Energy (DE-FG02- 03ER86169) through STTR grants to TDA Research, Inc. and CU Boulder. The authors also thank Dr. B. J. Elliott at TDA Research Inc., Prof. R. D. Noble at the University of Colorado at Boulder, and Prof. B. D. Freeman at the University of Texas at Austin for their in- valuable collaborative assistance in portions of this work. Finally, we thank Dr. W. Gu, Dr. T. J. Kidd, Dr. J. Jin, and Dr. J. Shailaja for their contributions to this research effort. FEATURE ARTICLE