Regulating C₂H₂/CO₂ adsorption selectivity by electronic-state manipulation of iron in metal-organic frameworks

The separation of C2H2 from C2H2/CO2 mixture is of great importance, yet highly challenging in the petrochemical industry due to their similar physicochemical properties. While open-metal sites (OMSs) in metal-organic frameworks (MOFs) are known to possess high affinity toward C2H2, its selective adsorption performance regulated by the electronic state of the same OMSs remains unexplored. Here, we report a metal electronic-state manipulation approach to construct a pair of isostructural Fe-MOFs, namely LIFM-26(Fe[II]/Fe[III]) and LIFM-27(Fe[III]) with different Fe[II] or Fe[III] oxidation states on the Fe centers, which display mixed-valent Fe[II]/Fe[III] centers in the former and sole Fe[III] centers in the latter. Remarkably, LIFM-26(Fe[II]/Fe[III]) shows significantly enhanced C2H2 uptake capacity than LIFM-27(Fe[III]), attested by adsorption isotherms and IAST calculations, as well as simulated and experimental breakthrough experiments. Furthermore, in situ infrared (IR) and molecular calculations unveil that the presence of Fe[II] in LIFM-26(Fe[II]/Fe[III]) results in stronger Fe[II]–C2H2 interactions than Fe[III]–C2H2, which plays a key role in the C2H2/CO2 separation

Hierarchically Patterned Elastomeric and Thermoplastic Polymer Films through Nanoimprinting and Ultraviolet Light Exposure

The surface relief structure of polymer films over large areas can be controlled by combining nanoscale imprinting and microscale ultraviolet-ozone (UVO) radiation, resulting in hierarchical structured surfaces. First, nanoscale patterns were formed by nanoimprinting elastomer [poly(dimethylsiloxane) (PDMS)] films with a pattern on a digital video disk. Micron-scale patterns were then superimposed on the nanoimprinted PDMS films by exposing them to ultraviolet radiation in oxygen (UVO) through a transmission electron microscopy grid mask having variable microscale patterning. UVO exposure leads to conversion and densification of PDMS to SiOx, leading to micron height relief features that follow a linear scaling relation with pattern dimension. Further, the pattern scopes are shown to collapse into a master curve by normalized feature values. Interestingly, these relief structures preserve the nanoscale features. In this paper, the influence of the self-limiting PDMS densification, wall stress at the boundary of micro-depression, and UVO exposure energy is studied in control of the micro-depression scale. This simple two-step imprinting process involving both nanoimprinting and UV radiation allows for facile fabrication of the dimension adjustable micro-nano hierarchically structures not only on elastomer films but also on thermoplastic polymer films. Coarse-grained molecular dynamics simulations were performed to correlate the surface tension and elastic properties of polymeric materials to the deformation of the pattern structure. � 2018 American Chemical Society.The authors wish to acknowledge Omnova Solutions Foundation, ACS#52997-ND7 Petroleum Research Foundation, NSF-DMR 1411046. The authors also extend their sincere appreciation to the Deanship of Scientific Research at King Saud University for its funding of this Prolific Research group (PRG-1436-14)

Enhanced strength, durability, and thermal shock resistance of clay roof tiles substituted with ferrosilicon slag

The present investigation involved the production of roof tile samples through the replacement of kaolin clay with varying proportions of Ferrosilicon slag (FS) (0%, 10%, 15%, 20%, and 25% by weight) at different firing temperatures (900 °C, 1000 °C, and 1100 °C). The present study investigated the impact of incorporating FS slag waste on durability, mechanical strength, thermal shock resistance, and thermal properties. Furthermore, an examination of the microstructure of the fired roof tiles was conducted through SEM analysis. The properties of the roof tiles exhibited enhancement as the percentage of FS slag increased, reaching a maximum of 15%, and the firing temperature increased up to 1000 °C. This can be attributed to the formation of significant amounts of corundum phase. Increased temperature and a higher percentage of FS slag are associated with the generation of a significant quantity of cristobalite phase, resulting in a reduction in the mechanical properties of roof tiles. The roof tile samples fabricated with up to 15% FS slag at 1000 °C exhibited low water absorption and porosity. Increases in temperature and FS slag, on the other hand, resulted in an increase in water absorption and porosity. There were no observable impacts on water absorption and apparent porosity at 900 °C. The firing temperature of 1000 °C and a slag percentage of 15% resulted in a minimum water absorption of 9.8%. This value meets the standard requirements for moderate weather resistance. Notwithstanding the increase in density of roof tiles containing elevated proportions of FS slag, they continue to fall within the limits of lightweight roof tiles as stipulated by determined standards. The experimental results indicate that the incorporation of 15% FS slag and firing at a temperature of 1000 °C resulted in a significant increase of 34.9% in the transverse breaking strength (TBS) of the clay roof tiles when compared to the conventional sample. This suggests that the structural properties of the clay roof tiles were improved through the addition of FS slag.Water Resource