Illuminating solid gas storage in confined spaces - methane hydrate formation in porous model carbons.

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.

Synthesis of Ordered Mesoporous Carbon Materials by Dry Etching.

A novel synthesis method for ordered mesoporous carbons is presented. The inverse replication of a silica template was achieved using the carbonization of sucrose within mesoporous KIT-6. Instead of liquid acid etching, as in classical nanocasting, a novel dry chlorine etching procedure for template removal is presented for the first time. The resultant ordered mesostructured carbon material outperforms carbons obtained by conventional hard templating with respect to high specific micro- and mesopore volumes (0.6 and 1.6 cm(3) g(-1) , respectively), due to the presence of a hierarchical pore system. A high specific surface area of 1671 m(2) g(-1) was achieved, rendering this synthesis route a highly convenient method to produce ordered mesoporous carbons.

Advanced structural analysis of nanoporous materials by thermal response measurements.

Thermal response measurements based on optical adsorption calorimetry are presented as a versatile tool for the time-saving and profound characterization of the pore structure of porous carbon-based materials. This technique measures the time-resolved temperature change of an adsorbent during adsorption of a test gas. Six carbide and carbon materials with well-defined nanopore architecture including micro- and/or mesopores are characterized by thermal response measurements based on n-butane and carbon dioxide as the test gases. With this tool, the pore systems of the model materials can be clearly distinguished and accurately analyzed. The obtained calorimetric data are correlated with the adsorption/desorption isotherms of the materials. The pore structures can be estimated from a single experiment due to different adsorption enthalpies/temperature increases in micro- and mesopores. Adsorption/desorption cycling of n-butane at 298 K/1 bar with increasing desorption time allows to determine the pore structure of the materials in more detail due to different equilibration times. Adsorption of the organic test gas at selected relative pressures reveals specific contributions of particular pore systems to the increase of the temperature of the samples and different adsorption mechanisms. The use of carbon dioxide as the test gas at 298 K/1 bar provides detailed insights into the ultramicropore structure of the materials because under these conditions the adsorption of this test gas is very sensitive to the presence of pores smaller than 0.7 nm.

Role of surface functional groups in ordered mesoporous carbide-derived carbon/ionic liquid electrolyte double-layer capacitor interfaces.

Ordered mesoporous carbide-derived carbon (OM-CDC) with a specific surface area as high as 2900 m(2) g(-1) was used as a model system in a supercapacitor setup based on an ionic liquid (IL; 1-ethyl-3-methylimidazolium tetrafluoroborate) electrolyte. Our study systematically investigates the effect of surface functional groups on IL-based carbon supercapacitors. Oxygen and chlorine functionalization was achieved by air oxidation and chlorine treatment, respectively, to introduce well-defined levels of polarity. The latter was analyzed by means of water physisorption isotherms at 298 K, and the functionalization level was quantified with X-ray photoelectron spectroscopy. While oxygen functionalization leads to a decreased capacitance at higher power densities, surface chlorination significantly improves the rate capability. A high specific capacitance of up to 203 F g(-1) was observed for a chlorinated OM-CDC sample with a drastically increased rate capability in a voltage range of ±3.4 V.

Stretchable and semitransparent conductive hybrid hydrogels for flexible supercapacitors.

Conductive polymers showing stretchable and transparent properties have received extensive attention due to their enormous potential in flexible electronic devices. Here, we demonstrate a facile and smart strategy for the preparation of structurally stretchable, electrically conductive, and optically semitransparent polyaniline-containing hybrid hydrogel networks as electrode, which show high-performances in supercapacitor application. Remarkably, the stability can extend up to 35,000 cycles at a high current density of 8 A/g, because of the combined structural advantages in terms of flexible polymer chains, highly interconnected pores, and excellent contact between the host and guest functional polymer phase.