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At least 577 records · Page 32

High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu 3 BTC 2 micropores

The host–guest system TCNQ@Cu 3 BTC 2 (TCNQ = 7,7,8,8-tetracyanoquinodimethane, BTC = 1,3,5-benzenetricarboxylate) is a striking example of how semiconductivity can be introduced by guest incorporation in an otherwise insulating parent material. Exhibiting both microporosity and semiconducting behavior such materials offer exciting opportunities as next-generation sensor materials. Here, we apply a solvent-free vapor phase loading under rigorous exclusion of moisture, obtaining a series of the general formula x TCNQ@Cu 3 BTC 2 (0 ≤ x ≤ 1.0). By using powder X-ray diffraction, infrared and X-ray absorption spectroscopy together with scanning electron microscopy and porosimetry, we provide the first structural evidence for a systematic preferential arrangement of TCNQ along the (111) lattice plane and the bridging coordination motif to two neighbouring Cu-paddlewheels, as was predicted by theory. For 1.0TCNQ@Cu 3 BTC 2 we find a specific electrical conductivity of up to 1.5 × 10 -4 S cm -1 whilst maintaining a high BET surface area of 573.7 m 2 g -1 . These values are unmatched by MOFs with equally high electrical conductivity, making the material attractive for applications such as super capacitors and chemiresistors. Our results represent the crucial missing link needed to firmly establish the structure–property relationship revealed in TCNQ@Cu 3 BTC 2 , thereby creating a sound basis for using this as a design principle for electrically conducting MOFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seismic refraction tracks porosity generation and possible CO 2 production at depth under a headwater catchment

Significance To understand groundwater in weathered bedrock aquifers, we explore (bio)geochemical reactions using geophysical measurements. The result leads to a conceptual model for the three-dimensional distribution of geochemical alteration in the subsurface—well beyond the typical approach of inferring (bio)geochemical reactions in the subsurface from pits, boreholes, and outcrops. With this geophysical technique we discovered the prevalence of gas beneath the water table at this site. This geophysical viewing of the subsurface highlights patterns of water movement, reactions of clays, and microbial and abiotic gas-producing reactions recorded in the subsurface and thus illuminates storage, flow, and reactions of groundwater in bedrock systems. Protecting the groundwater resource beneath our feet will rely on such enhanced capacities to see into the subsurface.

58 GEOSCIENCES↗

The dependence of tungsten fuzz layer thickness and porosity on tungsten deposition rate and helium ion fluence

Abstract Fuzz formation on a heated tungsten surface in the presence of a helium-containing plasma and tungsten deposition source was investigated. Tungsten samples were exposed at 1123 K to pure helium plasma with ion incident energy of 76 eV, W/He ion flux ratio of ∼ 0.4 × 10 − 4 , and varied helium ion fluence from 0.18 to 3.4 × 10 26 m −2 . Fuzz thickness was measured by cross-sectional scanning electron microscopy to increase from 0.22 to 15 µ m with increasing helium ion fluence. No indication of saturation in fuzz thickness at high fluence was observed, in contrast to fuzz produced on a tungsten surface without tungsten deposition. Additional tungsten samples were exposed at 1123 K to pure helium plasma with ion incident energy of 76 eV, helium ion fluence of ∼ 3.4 × 10 26 m −2 , and varied W/He ion flux ratio from 0.26 to 3.0 × 10 − 4 . Fuzz thickness increased from 7.5 to 120 µ m with increasing W/He ion ratio. A final sample exposed at 1123 K to a mixed helium-deuterium plasma with ion incident energy of 76 eV, helium ion fluence of 0.18 × 10 26 m −2 , and W/He ion flux ratio of 2.2 × 10 − 4 developed nearly identical fuzz structures to that developed in a pure He plasma. As a function of deposited tungsten fluence, all results were found to trace out a single layer-growth curve given by a power law relation, indicating that fuzz thickness is independent of the W/He ion flux ratio in the range investigated and independent of any deuterium present in the plasma. As a result, for tungsten plasma facing walls in magnetic fusion devices at 1000–2000 K with 10 −4 W/He ion flux ratio, fuzz with thicknesses greater than hundreds of microns may form in as little as 10 4 s (in the absence of ELM-induced erosion or annealing), and may more significantly affect its thermophysical properties than fuzz generated without a tungsten deposition source.

Physics↗