Hierarchically structured transparent hybrid membranes by in situ growth of mesostructured organosilica in host polymer

Abstract

The elaborate performances characterizing natural materials result from functional hierarchical constructions at scales ranging from nanometres to millimetres, each construction allowing the material to fit the physical or chemical demands occurring at these different levels. Hierarchically structured materials start to demonstrate a high input in numerous promising applied domains such as sensors, catalysis, optics, fuel cells, smart biologic and cosmetic vectors. In particular, hierarchical hybrid materials permit the accommodation of a maximum of elementary functions in a small volume, thereby optimizing complementary possibilities and properties between inorganic and organic components. The reported strategies combine sol-gel chemistry, self-assembly routes using templates that tune the material's architecture and texture with the use of larger inorganic, organic or biological templates such as latex, organogelator-derived fibres, nanolithographic techniques or controlled phase separation. We propose an approach to forming transparent hierarchical hybrid functionalized membranes using in situ generation of mesostructured hybrid phases inside a non-porogenic hydrophobic polymeric host matrix. We demonstrate that the control of the multiple affinities existing between organic and inorganic components allows us to design the length-scale partitioning of hybrid nanomaterials with tuned functionalities and desirable size organization from ångström to centimetre. After functionalization of the mesoporous hybrid silica component, the resulting membranes have good ionic conductivity offering interesting perspectives for the design of solid electrolytes, fuel cells and other ion-transport microdevices.

Lanthanide‐Containing Light‐Emitting Organic–Inorganic Hybrids: A Bet on the Future

“…We are currently in the age of ''tailor-made'' materials, exhibiting complex hierarchical structures and emergent properties. [139,140] The research carried out at present in the domain of hybridmaterials synthesis and self-assembly has helped to combine solid-state physics ''top-down'' methodologies with the molecular chemistry ''bottom-up'' approach. New hybrid materials have been produced through the spontaneous organization of BBs whose dimensions largely exceed those of the sub-nanometric scale of most molecules.…”

Nanoscopic Photoluminescence Memory as a Fingerprint of Complexity in Self‐Assembled Alkyl/Siloxane Hybrids

“…[3][4][5] The importance of combining sol-gel methods and self-assembly routes to synthesize hierarchically structured organic/inorganic materials, with potential applications in the design of ion-transport microdevices, has been highlighted recently.…”

“…[3][4][5] The importance of combining sol-gel methods and self-assembly routes to synthesize hierarchically structured organic/inorganic materials, with potential applications in the design of ion-transport microdevices, has been highlighted recently. [5] Silsesquioxanes ((RO) 3 -Si-R′-Si-(OR) 3 , where R and R′ are organic groups) and organosilanes (R′-Si-X 3 , where X = OR or Cl) are examples in which hierarchically ordered self-assembled architectures with well-defined morphologies at the macroscopic scale-such as ribbons stacked into lamellae, [6][7][8][9] 2D hexagonal structures, [9] twisted helical fibers with controlled handedness, [10] hollow tubes and spheres, [11] ladderlike superstructures, [12] and bilayered lamellar packing [13][14][15] are induced by weak interactions between the R′ organic spacers (hydrogen bonding, hydrophobic interactions, and p-p interactions).…”

Fractality and metastability of a complex amide cross-linked dipodal alkyl/siloxane hybrid

“…To generate other bilayer suprastructures displaying similar thermally activated photoluminescence memory effects and especially to lower the hysteretic range and thus yield materials mechanically more resistant to consecutive heating/cooling 40 cycles, several methodologies were subsequently adopted: (1) Changing the nature of the cross-link; 28 (2) Incorporating mono-, di-and trivalent salts; 29,30 -containing monoamidosils in a heating/cooling cycle are also reversible and timeindependent. Interestingly, these materials exhibit two distinct hysteresis domains, one associated with the order/disorder phase transition of the original lamellar bilayer structure of m-A (14) 65 and the second one associated with the order/disorder phase transition of the new lamellar bilayer structure which is formed in the presence of the guest salts.…”

“…1 Materials from the natural world are known to be complex systems 2,3 which provide plenty of inspiring examples of hierarchical 30 arrangement, 2,4,5 self-similarity growth6 and emergent phenomena. 7 Currently self-assembly stands as one of the few available practical approaches for organizing matter on large scales and the key driving force in the integration of natural and synthetic 35 …”