The nature of chemical bonding in the complex carbides Sc3[Fe(C2)2] (1) and Sc3[Co(C2)2] (2) has been explored by combined experimental and theoretical charge density studies. The structures of these organometallic carbides contain one-dimensional infinite TC4 (T = Fe, Co) ribbons embedded in a scandium matrix. Bonding in 1 and 2 was studied experimentally by multipolar refinements based on high-resolution X-ray data and compared to scalar-relativistic electronic structure calculations using the augmented spherical wave method. Besides substantial covalent T-C bonding within the TC4 ribbons, one also observes discrete Sc-C bonds of noticeable covalent character. Furthermore, our study highlights that even tiny differences in the electronic band structure of solids might be faithfully recovered in the properties of the Laplacian of the experimental electron density. In our case, the increase of the Fermi level in the organometallic Co(d9) carbide 2 relative to its isotypic Fe(d8) species 1 is reflected in the charge density picture by a significant change in the polarization pattern displayed by valence shell charge concentrations of the transition metal centers in the TC4 units. Hence, precise high-resolution X-ray diffraction data provide a reliable tool to discriminate and analyze the local electronic structures of isotypic solids, even in the presence of a severe coloring problem (Z(Fe)/Z(Co) = 26/27).
The electronic structures of the isotypic carbides Sc3TC4 (see picture; T=Fe, Co, Ni) are investigated by theoretical and experimental charge‐density studies. Even tiny differences in the electronic band structure of these solids are reflected in the properties of the Laplacian of the experimental electron density. Only the cobalt carbide is superconducting below 4.5 K and displays a structural phase transition around 70 K.
MgO sorbents doped with alkali-metal carbonates have been shown to exhibit improved sorption capacities at both low and moderate operating temperatures, compared to pure MgO sorbents. However, the mechanism of how alkali-metal carbonates enhance the CO2 sorption is not well understood. Using in situ X-ray diffraction, TEM, and thermogravimetric analysis, we have shown that the cesium dopants in the Cs2CO3-doped MgO nanoparticle system do not simply act as a promoter in sorption of CO2, but rather as a reagent alongside MgO. A new mixed magnesium–cesium carbonate phase has been found to be responsible for the improved sorption capacity of the doped-MgO-based sorbents. On the basis of our findings, it is suggested that a higher sorption capacity may be achieved if cesium is uniformly dispersed throughout the MgO particles.
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