Xiaoshuang Yang

Novel CaO-SiO2 sorbent and bifunctional Ni/Co-CaO/SiO2 complex for selective H2 synthesis from cellulose.

Catalysis- and sorption-enhanced biomass gasification is a promising route to high-purity hydrogen (H(2)); however, most CaO-based sorbents for CO(2) capture have poor surface area and mechanical properties, lose carrying capacity over multiple uses, and have insufficient porosity to accommodate extra catalyst sites. We aimed to develop a high-surface-area CaO-SiO(2) framework onto which catalysts could be grafted. The best CaO-SiO(2) sorbent (n(Ca)/n(Si) = 2:1) maintained a CaO conversion of 65% even after 50 carbonation-decarbonation cycles, better than commercial micrometer-sized CaO or tailored CaO, because of stabilization via Ca-O-Si interactions and an ordered porous structure. Bimetallic catalyst grains (Ni/Co alloy, <20 nm) could be evenly loaded onto this structure by impregnation. The resulting bifunctional complex produced H(2) at nearly the same rate as a mixture of catalyst and commercial CaO while using less total sorbent/catalyst. Furthermore, this complex was much more durable due to its higher coking resistance and stable structure. After 25 carbonation-decarbonation cycles, the new catalyst-sorbent complex enhanced the H(2) yield from cellulose far more than a mixture of catalyst and commercial CaO did following the same treatment.

Pretreatment Control of Carbon Nanotube Array Growth for Gas Separation: Alignment and Growth Studied Using Microscopy and Small-Angle X-ray Scattering

Aligned multiwalled carbon nanotube (CNT) arrays were prepared using chemical vapor deposition of C2H4 on Fe catalyst at 750 °C. CNT array height and alignment depends strongly on the duration of H2 pretreatment, with optimal height and alignment achieved using 10-15 min pretreatment. Small-angle X-ray scattering (SAXS) was used to quantify the alignment, distribution, and size of the CNTs in arrays produced from varying pretreatment times and the results correlated with microscopy measurements. SAXS analysis revealed that the higher section of the CNT arrays exhibited better alignment than the lower section. Combining these insights with transmission electron microscopy measurements of the CNT defects within each array enable a mechanism for the CNT growth to be proposed, where the loss of alignment arises from deformation of the CNTs during their growth. Gas permeation test across densified CNT arrays indicated that the alignment of the CNT array plays an important role in the gas transport, and that the gas diffusion across the well-aligned CNT arrays was enhanced by a factor of ~45, which is much more than that across the poorly aligned CNT arrays, with an enhancement factor of ~8.

Facile preparation of free-standing carbon nanotube arrays produced using two-step floating-ferrocene chemical vapor deposition.

A two-step floating-ferrocene chemical vapor deposition method has been devised for the preparation of single-layered aligned carbon nanotube (CNT) arrays. In the first step, uniform Fe catalysts are in situ produced and coated on a Si substrate from ferrocene; single-layered CNT arrays are prepared on these catalysts from ethylene in the second step. The effect of ferrocene loading on the distribution of Fe catalysts, as well as the morphology, diameter, and height of the CNT arrays, was investigated. A novel vacuum extraction process was employed to release the as-prepared CNT array from the Si wafer after water etching at 750 °C. The structural integrity of the free-standing arrays was preserved after the detachment process. The interface between the substrate and the as-grown CNT array was examined. The Fe catalyst distribution on the Si substrate remained homogeneous when the CNT array was removed, and the tops and bottoms of the arrays had different structures, suggesting that the arrays were formed predominantly by a base-growth mode. These free-standing arrays could potentially be applied in membrane or electronic applications.