The CO(2) adsorption characteristics of prototypical poly(ethyleneimine)/silica composite adsorbents can be drastically enhanced by altering the acid/base properties of the oxide support via incorporation of Zr into the silica support. Introduction of an optimal amount of Zr resulted in a significant improvement in the CO(2) capacity and amine efficiency under dilute (simulated flue gas) and ultradilute (simulated ambient air) conditions. Adsorption experiments combined with detailed characterization by thermogravimetric analysis, temperature-programmed desorption, and in situ FT-IR spectroscopy clearly demonstrate a stabilizing effect of amphoteric Zr sites that enhances the adsorbent capacity, regenerability, and stability over continued recycling. It is suggested that the important role of the surface properties of the oxide support in these polymer/oxide composite adsorbents has been largely overlooked and that the properties may be even further enhanced in the future by tuning the acid/base properties of the support.
Single-walled metal oxide (aluminosilicate) nanotubes are excellent candidates for addressing the long-standing issue of functionalizing nanotube interiors, due to their high surface reactivity and controllable dimensions. However, functionalization of the nanotube interior is impeded by its high surface silanol density (9.1 -OH/nm(2)) and resulting hydrophilicity. Controlled dehydration of the nanotubes is critical for the success of functionalization efforts. We employ a range of solid-state characterization tools to elucidate dehydration and dehydroxylation phenomena in the nanotubes as a function of heat treatment up to 450 degrees C. Vibrational spectroscopy (Fourier transform infrared, FT-IR), thermogravimetric analysis-mass spectrometry (TGA-MS), nitrogen physisorption, solid-state NMR, and X-ray diffraction (XRD) reveal that a completely dehydrated condition is achieved at 250 degrees C under vacuum and that the maximum pore volume is achieved at 300 degrees C under vacuum due to partial dehydroxylation of the dehydrated nanotube. Beyond 300 degrees C, further dehydroxylation partially disorders the nanotube wall structure. However, a unique rehydroxylation mechanism can partially reverse these structural changes upon re-exposure to water vapor. Finally, detailed XRD simulations and experiments allow further insight into the nanotube packing, the dimensions, and the dependence of nanotube XRD patterns on the water content.
Silica supported amine materials are promising compositions that can be used to effectively remove CO(2) from large stationary sources, such as flue gas generated from coal-fired power plants (ca. 10 % CO(2)) and potentially from ambient air (ca. 400 ppm CO(2)). The CO(2) adsorption characteristics of prototypical poly(ethyleneimine)-silica composite adsorbents can be significantly enhanced by altering the acid/base properties of the silica support by heteroatom incorporation into the silica matrix. In this study, an array of poly(ethyleneimine)-impregnated mesoporous silica SBA-15 materials containing heteroatoms (Al, Ti, Zr, and Ce) in their silica matrices are prepared and examined in adsorption experiments under conditions simulating flue gas (10 % CO(2) in Ar) and ambient air (400 ppm CO(2) in Ar) to assess the effects of heteroatom incorporation on the CO(2) adsorption properties. The structure of the composite adsorbents, including local information concerning the state of the incorporated heteroatoms and the overall surface properties of the silicate supports, are investigated in detail to draw a relationship between the adsorbent structure and CO(2) adsorption/desorption performance. The CO(2) adsorption/desorption kinetics are assessed by thermogravimetric analysis and in situ FT-IR measurements. These combined results, coupled with data on adsorbent regenerability, demonstrate a stabilizing effect of the heteroatoms on the poly(ethyleneimine), enhancing adsorbent capacity, adsorption kinetics, regenerability, and stability of the supported aminopolymers over continued cycling. It is suggested that the CO(2) adsorption performance of silica-aminopolymer composites may be further enhanced in the future by more precisely tuning the acid/base properties of the support.
We demonstrate new molecular-level concepts for constructing nanoscopic metal oxide objects. First, the diameters of metal oxide nanotubes are shaped with angstrom-level precision by controlling the shape of nanometer-scale precursors. Second, we measure (at the molecular level) the subtle relationships between precursor shape and structure and final nanotube curvature. Anionic ligands are used to exert fine control over precursor shapes, allowing assembly into nanotubes whose diameters relate directly to the curvatures of the 'shaped' precursors.
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