Publications by authors named "Bradley Bockrath"

Infrared spectroscopy is used to study trapped and physisorbed CO2 in single-walled carbon nanotube bundles (SWNTs) synthesized by the HiPco process. CO2 is entrapped within the SWNTs by acid oxidation of the unpurified sample followed by vacuum heating to 700 K. The trapped CO2 has a single nu3 mode at 2327 cm-1, is stable during temperature cycling from 77 to 700 K, and remains after venting to room air.

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Rare hysteretic adsorption/desorption isotherms are reported for CO2 and N2 on a pillared Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN)4] compound (NiBpeneNiCN). The hysteresis occurs under moderate pressure and at temperatures above the critical temperatures of the respective gases. Powder X-ray diffraction measurements indicate that the material is an extended three-dimensional analogue of the well-known Hofmann clathrates which is formed through axial bridging of the in-plane octahedral Ni sites by the bidentate 1,2-bis(4-pyridyl)ethylene.

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Fourier transform infrared spectroscopy is used to study CO adsorption in single-walled carbon nanotubes. Evidence for adsorption in endohedral and groove/external surface sites is presented through displacement studies involving both CO and CO2. Blue-shifted CO stretching frequencies also indicate that CO hydrogen bonds to hydroxyl functionalities created on the nanotubes by acid purification steps.

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A simple procedure is described that locks small quantities of SF6, CO2, and 13CO2 into opened single-walled carbon nanotube (SWNT) bundles and keeps the gas in the SWNTs above the desorption temperature of these molecules. The technique involves opening the SWNTs with ozonolysis at 300 K followed by vacuum-annealing at 700 K. Gases are then cryogenically adsorbed into the opened SWNTs and locked into the SWNT pores by functionalizing the sample with a low-temperature ozone treatment.

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The volumetric hydrogen adsorption isotherms of two isostructural dehydrated cubic metal nitroprussides M[Fe(CN)5NO] (M = Co2+, Ni2+) have been measured up to a pressure of 760 Torr at 77 and 87 K. These materials are among the most efficient H2 sorbents based on porous coordination polymers reported to date. The H2 uptake in both materials is approximately 1.

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Raman spectroscopy has been used to investigate ethane, propane, and SF6 interactions with an aligned multiwalled carbon nanotube (MWNT) membrane. Pressures of 7.5-9.

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Heretofore disconnected experimental observations are combined with a theoretical study to develop a model of the chemical composition of the edges of graphene sheets in both flat and curved sp(2)-hybridized carbon materials. It is proposed that under ambient conditions a significant fraction of the oxygen-free edge sites are neither H-terminated nor unadulterated sigma free radicals, as universally assumed. The zigzag sites are carbene-like, with the triplet ground state being most common.

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Advancement in hydrogen storage techniques represents one of the most important areas of today's materials research. While extensive efforts have been made to the existing techniques, there is no viable storage technology capable of meeting the DOE cost and performance targets at the present time. New materials with significantly improved hydrogen adsorption capability are needed.

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