Mesoporous organic-inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co-condensation, one-pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.

Silica-based mesoporous organic-inorganic hybrid materials.

Metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) are open, crystalline supramolecular coordination architectures with porous facets. These chemically tailorable framework materials are the subject of intense and expansive research, and are particularly relevant in the fields of sensory materials and device engineering. As the subfield of MOF-based sensing has developed, many diverse chemical functionalities have been carefully and rationally implanted into the coordination nanospace of MOF materials. MOFs with widely varied fluorometric sensing properties have been developed using the design principles of crystal engineering and structure–property correlations, resulting in a large and rapidly growing body of literature. This work has led to advancements in a number of crucial sensing domains, including biomolecules, environmental toxins, explosives, ionic species, and many others. Furthermore, new classes of MOF sensory materials utilizing advanced signal transduction by devices based on MOF photonic crystals and thin films have been developed. This comprehensive review summarizes the topical developments in the field of luminescent MOF and MOF-based photonic crystals/thin film sensory materials.

Metal-organic frameworks: functional luminescent and photonic materials for sensing applications.

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Conductometric semiconducting metal oxide gas sensors have been widely used and investigated in the detection of gases. Investigations have indicated that the gas sensing process is strongly related to surface reactions, so one of the important parameters of gas sensors, the sensitivity of the metal oxide based materials, will change with the factors influencing the surface reactions, such as chemical components, surface-modification and microstructures of sensing layers, temperature and humidity. In this brief review, attention will be focused on changes of sensitivity of conductometric semiconducting metal oxide gas sensors due to the five factors mentioned above.

Metal oxide gas sensors: Sensitivity and influencing factors

In this review, the progress made in the last ten years concerning the synthesis of porous carbon materials is summarized. Porous carbon materials with various pore sizes and pore structures have been synthesized using several different routes. Microporous activated carbons have been synthesized through the activation process. Ordered microporous carbon materials have been synthesized using zeolites as templates. Mesoporous carbons with a disordered pore structure have been synthesized using various methods, including catalytic activation using metal species, carbonization of polymer/polymer blends, carbonization of organic aerogels, and template synthesis using silica nanoparticles. Ordered mesoporous carbons with various pore structures have been synthesized using mesoporous silica materials such as MCM-48, HMS, SBA-15, MCF, and MSU-X as templates. Ordered mesoporous carbons with graphitic pore walls have been synthesized using soft-carbon sources that can be converted to highly ordered graphite at high temperature. Hierarchically ordered mesoporous carbon materials have been synthesized using various designed silica templates. Some of these mesoporous carbon materials have successfully been used as adsorbents for bulky pollutants, as electrodes for supercapacitors and fuel cells, and as hosts for enzyme immobilization. Ordered macroporous carbon materials have been synthesized using colloidal crystals as templates. One-dimensional carbon nanostructured materials have been fabricated using anodic aluminum oxide (AAO) as a template.

Recent Progress in the Synthesis of Porous Carbon Materials

Semiconducting metal oxides are frequently used as gas-sensing materials. Apart from large surface-to-volume ratios, well-defined and uniform pore structures are particularly desired for improved sensing performance. This article addresses the role of some key structural aspects in porous gas sensors, such as grain size and agglomeration, pore size or crack-free film morphology. New synthesis concepts, for example, the utilisation of rigid matrices for structure replication, allow to control these parameters independently, providing the opportunity to create self-diagnostic sensors with enhanced sensitivity and reproducible selectivity.

Porous Metal Oxides as Gas Sensors

Ordered mesoporous materials have great potential in the field of gas sensing. Today various template-assisted synthesis methods facilitate the preparation of silica (SiO2) as well as numerous metal oxides with well-defined, uniform and regular pore systems. The unique nanostructural properties of such materials are particularly useful for their application as active layers in gas sensors based on various operating principles, such as capacitive, resistive, or optical sensing. This review summarizes the basic aspects of materials synthesis, discusses some structural properties relevant in gas sensing, and gives an overview of the literature on ordered mesoporous gas sensors.

Mesoporous materials as gas sensors

The synthesis and characterization of ordered mesoporous In2O3 materials by structure replication from hexagonal mesoporous SBA-15 silica and cubic KIT-6 silica is presented. Variation of the synthesis parameters allows for different pore sizes and pore wall thicknesses in the products. The In2O3 samples turn out to be stable up to temperatures between 450 °C and 650 °C; such high thermal stability is necessary for their application as gas sensors. Test measurements show a high sensitivity to methane gas in concentrations relevant for explosion prevention. The sensitivity is shown to be correlated not only with the surface-to-volume ratio, but also with the nanoscopic structural properties of the materials.

Ordered Mesoporous In2O3: Synthesis by Structure Replication and Application as a Methane Gas Sensor

Periodically ordered mesoporous magnesium oxides were synthesized by utilization of mesoporous CMK-3 carbon as exotemplate. The products exhibit high thermal stability and basic properties, which makes them promising for application in heterogeneous basic catalysis.

Ordered mesoporous magnesium oxide with high thermal stability synthesized by exotemplating using CMK-3 carbon.

Periodically ordered mesoporous magnesium oxide was synthesized in a double replication procedure. Mesoporous SBA-15 silica and CMK-3 carbon were successively used as hard structure matrixes. The carbon pore system was infiltrated with Mg(NO3)2, which was then converted to MgO at 573 K; the carbon matrix was finally removed by thermal combustion. The structure of the mesoporous MgO corresponds to that of the original SBA-15 silica. The products consist of hexagonally arranged cylindrical mesopores and crystalline pore walls. The efficiency of the replication series was studied by variation of the infiltration method and comprehensive pore size analysis of all involved mesoporous materials. The in situ formation of MgO inside the CMK-3 carbon pore system was monitored by thermal analysis. Postsynthetic treatment of the products at 823 K in a vacuum prior to removal of the carbon matrix was found to improve the crystallinity but to diminish the periodic order of the pore system.

Michael Tiemann

Papers

Porous Metal Oxides as Gas Sensors

Mesoporous materials as gas sensors

Ordered Mesoporous In2O3: Synthesis by Structure Replication and Application as a Methane Gas Sensor

Ordered mesoporous magnesium oxide with high thermal stability synthesized by exotemplating using CMK-3 carbon.

Synthesis of mesoporous magnesium oxide by CMK-3 carbon structure replication