In situ activation of green sorbents for CO2 capture upon end group backbiting.

Thermolysis of a urethane end group was observed as a first time phenomenon during activation. This unzipping mechanism revealed a new amine tethering point producing a diamine-terminated oligourea ([10]-OU), acting as a green sorbent for CO2 capturing. The oligomer backbites its end group to form propylene carbonate (PC), as proved by in situ TGA-MS, which can reflect the polymer performance by maximizing its capturing capacity. Cross polarization magic angle spinning (CP-MAS) NMR spectroscopy verified the formation of the proven ionic carbamate (1:2 mechanism) with a chemical shift at 161.7 ppm due to activation desorption at higher temperatures, viz., 100 °C (in vacuo) accompanied with bicarbonate ions (1:1 mechanism) with a peak centered at 164.9 ppm. Fortunately, the amines formed from in situ thermolysis explain the abnormal behavior (carbamates versus bicarbonates) of the prepared sample. Finally, ex situ ATR-FTIR proved the decomposition of urethanes, which can be confirmed by the disappearance of the pre-assigned peak centered at 1691 cm-1. DFT calculations supported the thermolysis of the urethane end group at elevated temperatures, and provided structural insights into the formed products.

[n]-Oligourea-Based Green Sorbents with Enhanced CO2 Sorption Capacity.

A new series of [n]-oligoureas ([n]-OUs, n=4, 7, 10, and 12) green solid sorbents was prepared following a base-catalyzed, microwave-assisted oligomerization reaction. The materials were characterized by NMR and IR spectroscopy, elemental analysis, thermogravimetric analysis, differential scanning calorimetry, and XRD. Decomposition temperatures at 50 % weight loss (Td50 ) were ca. 350 °C for all oligomers. Urea and urethane functional groups indicated by IR spectroscopy confirmed the formation of the sorbent. The CO2 capturing capacities were determined at 35 °C and 1.0 bar (gravimetric method). Accordingly, [10]-OU had the highest CO2 sorption capacity among the others (18.90 and 22.70 mg CO 2 gsorbent (-1) ) at two different activation temperatures (60 or 100 °C, respectively). Chemisorption was the principal mechanism for CO2 capture. Cyclic CO2 sorption/desorption measurements were carried out to test the recyclability of [10]-OU. Activating the sample at 60 °C, three stable CO2 sorption cycles were achieved after running the first cycle.

Ordered mesoporous silica prepared by quiescent interfacial growth method - effects of reaction chemistry.

Acidic interfacial growth can provide a number of industrially important mesoporous silica morphologies including fibers, spheres, and other rich shapes. Studying the reaction chemistry under quiescent (no mixing) conditions is important for understanding and for the production of the desired shapes. The focus of this work is to understand the effect of a number of previously untested conditions: acid type (HCl, HNO3, and H2SO4), acid content, silica precursor type (TBOS and TEOS), and surfactant type (CTAB, Tween 20, and Tween 80) on the shape and structure of products formed under quiescent two-phase interfacial configuration. Results show that the quiescent growth is typically slow due to the absence of mixing. The whole process of product formation and pore structuring becomes limited by the slow interfacial diffusion of silica source. TBOS-CTAB-HCl was the typical combination to produce fibers with high order in the interfacial region. The use of other acids (HNO3 and H2SO4), a less hydrophobic silica source (TEOS), and/or a neutral surfactant (Tweens) facilitate diffusion and homogenous supply of silica source into the bulk phase and give spheres and gyroids with low mesoporous order. The results suggest two distinct regions for silica growth (interfacial region and bulk region) in which the rate of solvent evaporation and local concentration affect the speed and dimension of growth. A combined mechanism for the interfacial bulk growth of mesoporous silica under quiescent conditions is proposed.

Gas diffusion and microstructural properties of ordered mesoporous silica fibers.

Pore and surface diffusion of carbon dioxide (CO(2)) and ethylene (C(2)H(4)) in the nanopores of ordered mesoporous silica fibers about 200 microm in length was measured by the transient gravimetric method. The experimentally determined pore diffusivity data, coupled with the porosity, pore size, and fiber length, are used to obtain the actual length of the nanopores in silica fibers. These measurements reveal a structure of the ordered nanopores whirling helically around the fiber axis with a spiral diameter of about 15 microm and a pitch value of 1.6 microm. At room temperature the surface diffusion contributes about 10% to the total diffusional flux for these two gases in the nanopores of the ordered mesoporous silica fibers. The surface diffusion coefficients for the ordered mesoporous silica fibers are about 1 order of magnitude larger than the non-ordered mesoporous alumina or silica with similar pore size.