Beside IGCC, efficient storage and transportation of CO2 and other gases require pressurize conditions. CO2 and other gases adsorption on solid sorbents at high pressure and various temperatures are extremely important as long as the environmental purification via gas capture and separation and gas transpiration are concern. The main objective of the present research was to investigate the effect of amine impregnation on the CO2, methane and nitrogen adsorption capacity of mesoporous silica (SBA-15). Ordered mesoporous silica (SBA-15) was prepared and modified with ammonium hydroxide solution to introduce NH2 functional groups within the pores of materials to produce modified SBA-15 (MSBA-15). The newly prepared materials were characterized with X-ray diffraction analysis, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis were performed to measure pore volume as well as the surface area of both the unmodified and modified samples. Results revealed that the crystal structures of SBA-15 were matched with that of MSBA15; yet, pore volume of the modified material was almost reduced to 50% of the pristine material indicating amine loading into the pore channels. Importantly, gas sorption capacity was investigated at 200bars and three different temperatures of 318K, 328K, and 338K by using state-of-the-art gravimetric Rubotherm® magnetic suspension sorption apparatus. Gas sorption experiments showed that modified mesoporous silica adsorbed 1.6164mmol/g of CO2 at 1bar which is almost double than that of 0.6462mmol/g adsorbed by unmodified material. Quantitative selectivity of both the materials varied as CO2>CH4>N2
Covalent organic polymer framework with C-C bonds as a fluorescent probe for selective iron detection
A new carbon–carbon bonded nanoporous polymer network was synthesized via efficient and catalyst free Knoevenagel-like condensation polymerization in near quantitative yields. The obtained polymer network, Covalent Organic Polymer – COP-100 possesses strong fluorescent properties and designed solubility in polar aprotic solvents, which shows promise for use as a metal-sensing material in solution. COP-100 exhibited high selectivity towards Fe2+ and Fe3+ in the presence of other common metal cations (Al3+, Ag+, Cd2+, Co2+, Cr3+, Cu2+, Hg2+, Mg2+, Mn2+, Na+, Ni2+, Zn2+) as the fluorescence of the polymer was significantly quenched even at very low concentrations. In the range from 2.5 × 10−6 to 2 × 10−4 M, a linear fluorescence emission response with equipment limited detection minimum of 2.13 × 10−7 M and 2.45 × 10−7 M for Fe2+ and Fe3+, respectively, was observed. These results suggest that COP-100 is a promising material as a selective fluorescence sensor for iron ions.
Systematic investigation of the effect of polymerization routes on the gas sorption properties of nanoporous azobenzene polymers
O. Buyukcakir, S. H. Je, J. Park, H. A. Patel, Y. Jung, C. T. Yavuz, A. Coskun
Same but different: Chemically similar nanoporous azobenzene polymers that are synthesized by using different polymerization routes show completely different gas-sorption characteristics (see figure). Pore widths of 6–8 Å and small particle sizes are very critical for high CO2/N2 selectivity. Furthermore, N2 phobicity is associated with the azo linkages and is realized at warm temperatures.
Highly optimized CO2 capture by inexpensive nanoporous covalent organic polymers and their amine composites
Carbon dioxide (CO2) storage and utilization requires effective capture strategies that limit energy penalties. Polyethylenimine (PEI)-impregnated covalent organic polymers (COPs) with a high CO2 adsorption capacity are successfully prepared in this study. A low cost COP with a high specific surface area is suitable for PEI loading to achieve high CO2 adsorption, and the optimal PEI loading is 36 wt%. Though the adsorbed amount of CO2 on amine impregnated COPs slightly decreased with increasing adsorption temperature, CO2/N2 selectivity is significantly improved at higher temperatures. The adsorption of CO2 on the sorbent is very fast, and a sorption equilibrium (10% wt) was achieved within 5 min at 313 K under the flow of simulated flue gas streams. The CO2 capture efficiency of this sorbent is not affected under repetitive adsorption–desorption cycles. The highest CO2 capture capacity of 75 mg g−1 at 0.15 bar is achieved under dry CO2 capture however it is enhanced to 100 mg g−1 in the mixed gas flow containing humid 15% CO2. Sorbents were found to be thermally stable up to at least 200 °C. TGA and FTIR studies confirmed the loading of PEIs on COPs. This sorbent with high and fast CO2 sorption exhibits a very promising application in direct CO2 capture from flue gas.
Nanoporous networks as caging supports for uniform, surfactant-free Co3O4 nanocrystals and their applications in energy storage and conversion
J. Byun, H. A. Patel, D. J. Kim, C. H. Jung, J. Y. Park, J. W. Choi, C. T. Yavuz
We report a new, surfactant-free method to produce Co3O4 nanocrystals with controlled sizes and high dispersity by caging templation of nanoporous networks. The morphologies of Co3O4 nanoparticles differ from wires to particulates by simply varying solvents. The composites of nanoparticles within network polymers are highly porous and are promising for many applications where accessible surface and aggregation prevention are important. The electrochemical performance of the composites demonstrates superior capacity and cyclic stability at a high current density (∼980 mA h g−1 at the 60th cycle at a current density of 1000 mA g−1). In a catalytic oxidation reaction of carbon monoxide, the composites exhibit a remarkable stability (in excess of 35 hours) and catalytic performance (T100 = 100 °C).
Influence of interlayer functionalization of kaolinite on property profile of copolymer nanocomposites
S. Zulfiqar, M. I. Sarwar, N. Rasheed, C. T. Yavuz
Nanocomposites of co-poly (vinyl chloride–polyvinyl acetate–polyvinyl alcohol) (PVC–PVAc–PVA) and kaolinite were prepared via solution intercalation technique. To improve compatibility among the phases and to expand the interlayer basal spacing, kaolinite was modified using dimethylsulfoxide (DMSO) as a swelling agent. The influence of kaolinite dispersion and interaction between the disparate phases on the properties of nanocomposites were investigated using Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), mechanical testing, thermogravimetric analysis (TGA) and water absorption measurements. IR data confirmed the hydrogen bonds formed between DMSO and the surface hydroxyl groups of kaolinite. XRD and microscopic results revealed that clay mineral was intercalated with uniform dispersion at nanoscale in the matrix. Tensile testing of these materials indicated significant improvements in the mechanical properties relative to the pure copolymer. Incorporation of kaolinite into the organic phase enhanced the thermal stability of the nanocomposites. Water absorption of the nanomaterials was reduced upon the addition of modified kaolinite rendering decreased permeability with increasing dispersibility of clay mineral in the copolymer matrix.
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