Hybrid Inorganic–Organic Mesoporous Silicates—Nanoscopic Reactors Coming of Age

This review describes methods of preparing hybrid inorganic–organic mesoporous silicates with uniform channel structures, as well as some of their applications. Both reactive and passive organic groups can be incorporated in the porous solids by grafting methods or by co‐condensation under surfactant control. Functional groups have been placed selectively on the internal or external pore surfaces or even within the walls of the mesoporous solids. Organic functionalization of these solids permits tuning of the surface properties (hydrophilicity, hydrophobicity, binding to guest molecules), alteration of the surface reactivity, protection of the surface from attack, and modification of the bulk properties (e.g., mechanical or optical properties) of the material. Recent applications of hybrid mesoporous silicates are highlighted, including catalysis, sorption of metals, anions, and organics, reactors for polymerization, fixation of biologically active species, and optical applications.     

Calcium Carbonate–Organic Hybrid Materials

This article focuses on the synthetic approach to the preparation of calcium carbonate–organic hybrid materials, which are obtained by self‐organization processes under mild conditions. In these processes, organic molecules such as functionalized polymers and aligned amphiphilic molecules on the surface play key roles in the crystallization of calcium carbonate, which results in the formation of hybrid materials. As well as being environmentally benign, the hybrid materials have controlled morphology and unique properties. Materials scientists have obtained the ideas for the design of such hybrid materials from biominerals such as shells, teeth, and bones.     

Carbosilane Dendrimers as Nanoscopic Building Blocks for Hybrid Organic–Inorganic Materials and Catalyst Supports

Advanced nanoarchitectures can be achieved by covalent linking of dendrimeric modules into porous networks using sol–gel chemistry. The focus of this work lies in the conversion of second, third, and fourth generation carbosilane dendrimers to high surface area xerogels and aerogels, and the use of these materials as catalyst supports. By varying the hydrolysis solvent and dendrimeric precursor employed, the properties of the nanoarchitectures can be easily tuned. In particular, triethoxysilyl‐terminated dendrimers have been hydrolyzed in solvents of varying polarity with acid catalysts to produce micro‐ and mesoporous hybrid dendrimer xerogels and aerogels with a controllable degree of Si–OH functionality.     

A Cut‐and‐Weld Process to 3D Architectures from Multiresponsive Crosslinked Liquid Crystalline Polymers

Crosslinked liquid crystalline polymers (CLCPs) have garnered extensive attention in recent years for their significant values in the design of light‐driven soft actuators. However, poor processabilities due to the insoluble and infusible crosslinked networks prevent their practical applications severely. In this study, a weldable azobenzene‐containing CLCP is designed with photo‐ and humidity‐responsive actuations, which enables a cut‐and‐weld process to 3D CLCP architectures. The tensile properties and stability are almost unchanged after welding, much better than those of the films pasted by common adhesive tapes. Meanwhile, the mechanisms of the welding process are clarified on the base of surface hydrogen bonding and further crosslinking. By taking advantage of the cut‐and‐weld process, a 3D “claw” integrated into a robotic arm is realized for grabbing millimeter‐scale objects by remote control. This work enhances significantly not only the processability of CLCP films but also the utilization of leftover pieces, which provides an efficient approach to create functional 3D structures from film precursors for the potential application in the smart materials.     

Nanostructured Metal–Organic Conjugated Coordination Polymers with Ligand Tailoring for Superior Rechargeable Energy Storage

Conjugated coordination polymers have become an emerging category of redox‐active materials. Although recent studies heavily focus on the tailoring of metal centers in the complexes to achieve stable electrochemical performance, the effect on different substitutions of the bridging bonds has rarely been studied. An innovative tailoring strategy is presented toward the enhancement of the capacity storage and the stability of metal–organic conjugated coordination polymers. Two nanostructured d‐π conjugated compounds, Ni[C₆H₂(NH)₄]_n (Ni‐NH) and Ni[C₆H₂(NH)₂S₂]_n (Ni‐S), are evaluated and demonstrated to exhibit hybrid electrochemical processes. In particular, Ni‐S delivers a high reversible capacity of 1164 mAh g^?1, an ultralong stability up to 1500 cycles, and a fully recharge ability in 67 s. This tailoring strategy provides a guideline to design future effective conjugated coordination‐polymer‐based electrodes.