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An emerging class of materials that are hybrid in nature is propelling a technological revolution in energy, touching many fundamental aspects of energy-generation, storage, and conservation. Hybrid materials combine classical inorganic and organic components to yield materials that manifest new functionalities unattainable in traditional composites or other related multicomponent materials, which have additive function only. This Research News article highlights the exciting materials design innovations that hybrid materials enable, with an eye toward energy-relevant applications involving charge, heat, and mass transport.

Hydrogen is a promising alternative energy carrier that can potentially facilitate the transition from fossil fuels to sources of clean energy because of its prominent advantages such as high energy density (142 MJ kg(-1); ref. 1), great variety of potential sources (for example water, biomass, organic matter), light weight, and low environmental impact (water is the sole combustion product). However, there remains a challenge to produce a material capable of simultaneously optimizing two conflicting criteria--absorbing hydrogen strongly enough to form a stable thermodynamic state, but weakly enough to release it on-demand with a small temperature rise. Many materials under development, including metal-organic frameworks, nanoporous polymers, and other carbon-based materials, physisorb only a small amount of hydrogen (typically 1-2 wt%) at room temperature. Metal hydrides were traditionally thought to be unsuitable materials because of their high bond formation enthalpies (for example MgH(2) has a ΔHf~75 kJ mol(-1)), thus requiring unacceptably high release temperatures resulting in low energy efficiency. However, recent theoretical calculations and metal-catalysed thin-film studies have shown that microstructuring of these materials can enhance the kinetics by decreasing diffusion path lengths for hydrogen and decreasing the required thickness of the poorly permeable hydride layer that forms during absorption. Here, we report the synthesis of an air-stable composite material that consists of metallic Mg nanocrystals (NCs) in a gas-barrier polymer matrix that enables both the storage of a high density of hydrogen (up to 6 wt% of Mg, 4 wt% for the composite) and rapid kinetics (loading in

Sensing ofthe volatile organic compounds (VOCs) isopropyl alcohol (IPA) and heptane in air using sub-millimeter porous silicon-based sensor elements is demonstrated in the concentration range 50-800 ppm. The sensor elements are prepared as one-dimensional photonic crystals (rugate filters) by programmed electrochemical etch of p ++ silicon, and analyte sensing is achieved by measurement of the wavelength shift of the photonic resonance. The sensors are studied as a function of surface chemistry: ozone oxidation, thermal oxidation, hydrosilylation (1-dodecene), electrochemical methylation, reaction with dicholorodimethylsilane and thermal carbonization with acetylene. The thermally oxidized and the dichlorodimethylsilane-modified materials show the greatest stability under atmospheric conditions. Optical microsensors are prepared by attachment of the porous Si layer to the distal end of optical fibers. The acetylated porous Si microsensor displays a greater response to heptane than to IPA, whereas the other chemical modifications display a greater response to IPA than to heptane. The thermal oxide sensor displays a strong response to water vapor, while the acetylated material shows a relatively weak response. The results suggest that a combination of optical fiber sensors with different surface chemistries can be used to classify VOC analytes. Application of the miniature sensors to the detection of VOC breakthrough in a full-scale activated carbon respirator cartridge simulator is demonstrated.

One-dimensional photonic crystals constructed from multilayered stacks of porous Si are used as sensors for gas-phase volatile organic compounds (VOCs). The ability of a double-stack structure to provide compensation for drift due to changing relative humidity (RH) is investigated. In this approach, two separate photonic crystals (dielectric stacks) are etched into a crystalline Si substrate, one on top of the other. The top stack is chemically modified to be hydrophobic (by hydrosilylation with dodecene) and the bottom stack is made hydrophilic (by hydrosilylation with undecylenic acid). It is shown that the optical spectrum of the double-stack structure provides an effective means to discriminate VOCs from water vapor. In this approach, shifts in the peak frequencies from both photonic crystals are measured simultaneously. Because the two stacks respond differently to water and to VOC, the effect of changing humidity can be nulled by calculating the weighted difference between the two peak frequencies. Reliable determination of the concentration of VOC vapor in nitrogen over a range of RH values (25%

Hydron exchange reaction rates, k(exch)M(-1) s(-1), using methanolic sodium methoxide are compared with gas-phase acidities, Delta G(Acid)(0) kcal/mol, for four 9-YPhenylfluorenes-9-H-i, seven (YC6H4CH)-H-i(CF3)(2), seven YC6H4-(CHClCF3)-H-i, and (C6F5H)-H-i. Fourteen of the fluorinated benzylic compounds and pentafluorobenzene result in near unity experimental hydrogen isotope effects that suggest substantial amounts of internal return associated with the exchange process. Although the reactions of 9-phenylfluorene have experimental isotope effects that appear to be normal in value, they do not obey the Swain-Schaad relationship. This suggests that they occur with small amounts of internal return. The entropies of activation, Delta S-double dagger, are +12 to +14eu, for the benzylic compounds and different significantly from those for the 9-YPhenylfluorenes, Delta S-double dagger of -8 to - 12 eu. The Delta S-double dagger similar to 1 eu for the reactions of pentafluorobenzene falls between the other compounds. Density functional calculations using B3LYP/6-31+G(d,p) are reported for the reactions of CH3O-(HOCH3)(3) with C6F5H, C6H5CH(CF3)(2), C6H5CHClCF3, and 9-phenylfluorene. Copyright (c) 2006 John Wiley & Sons, Ltd.

The role of encapsulating polymers in nanocrystalline Mg air stability and hydrogen storage density was studied for a series of composites varying in both % Mg and polymer identity. In these materials, the Mg nanocrystals are completely dependent on the polymer for air stability. Remarkably, both air stability and hydrogen sorption capacity of poly(methyl methacrylate) composites were enhanced by reducing the amount of polymer. Composites consisting of 65 wt% Mg absorbed 6.95 wt% hydrogen and showed little oxidation after 3 months air exposure even after enduring the volume expansion induced by hydrogen sorption, whereas composites with 33.2 wt% Mg absorbed just 4.86 wt% hydrogen and were completely oxidized upon air exposure after hydrogen sorption. This surprising synergistic enhancement in stability and storage density is attributed to an increase in the tortuosity of the paths of gas molecules and increased interfacial structure-templating regions, which scale with % Mg loading and lead to nanoparticle entanglements, hindering polymer chain motion.

The carbon dioxide storage capacity of magnesium oxide (MgO) particles was examined as a function of particle size, shape, and surface area. Two types of MgO nanocrystals (5 nm spheres and 23 nm disks) were synthesized and compared against commercially available MgO (325 mesh/44 μm and 40 mesh/420 μm). The surface area of the four types of particles was determined by N2 gas adsorption. Carbon dioxide capture was measured at 60 °C and 600 °C using thermogravimetric analysis, with results indicating enhanced CO2 capacity correlating with increased surface area.