From Synthesis to Microstructure: Engineering the High-entropy Ceramic Materials of the Future.

Sintering and microstructural development in ceramics has long been studied in a two-dimensional grain size-density space, with only texture (i.e. deviation of grain orientation from random) used to gain first insights into additional parametric spaces. Following an increased interest for grain boundary engineering and a deeper understanding of dopant effects on sintering and grain boundaries, the theory of complexion transitions for ceramics has been introduced over the last decade, providing a new base for advanced microstructure engineering in ceramics. With emergence of high entropy ceramics over the last 5 years, the combination of both yields new grounds for exploration and engineering of functional ceramic materials of the future.

Carbohydrate-mediated purification of petrochemicals.

Metal-organic frameworks (MOFs) are known to facilitate energy-efficient separations of important industrial chemical feedstocks. Here, we report how a class of green MOFs-namely CD-MOFs-exhibits high shape selectivity toward aromatic hydrocarbons. CD-MOFs, which consist of an extended porous network of γ-cyclodextrins (γ-CDs) and alkali metal cations, can separate a wide range of benzenoid compounds as a result of their relative orientation and packing within the transverse channels formed from linking (γ-CD)6 body-centered cuboids in three dimensions. Adsorption isotherms and liquid-phase chromatographic measurements indicate a retention order of ortho- > meta- > para-xylene. The persistence of this regioselectivity is also observed during the liquid-phase chromatography of the ethyltoluene and cymene regioisomers. In addition, molecular shape-sorting within CD-MOFs facilitates the separation of the industrially relevant BTEX (benzene, toluene, ethylbenzene, and xylene isomers) mixture. The high resolution and large separation factors exhibited by CD-MOFs for benzene and these alkylaromatics provide an efficient, reliable, and green alternative to current isolation protocols. Furthermore, the isolation of the regioisomers of (i) ethyltoluene and (ii) cymene, together with the purification of (iii) cumene from its major impurities (benzene, n-propylbenzene, and diisopropylbenzene) highlight the specificity of the shape selectivity exhibited by CD-MOFs. Grand canonical Monte Carlo simulations and single component static vapor adsorption isotherms and kinetics reveal the origin of the shape selectivity and provide insight into the capability of CD-MOFs to serve as versatile separation platforms derived from renewable sources.

Spectroelectrochemical study of carbon structural and functionality characteristics on vanadium redox reactions for flow batteries.

Vanadium redox flow batteries have applications for large-scale electricity storage. This paper reports the influence of carbon structural characteristics of sustainable walnut shell-derived carbons in carbon/polyvinylidene fluoride composite electrodes on vanadium redox reactions. Pyrolysis, gasification, and chemical treatment procedures were used to modify the structural characteristics of carbons. Carbon functional groups were modified by chemical treatment with HNO3, heat treatment with K2CO3, and high-temperature NH3 treatment. Carbon porous structures were characterized using gas adsorption studies. Raman spectroscopy and X-ray diffraction were used to characterize the carbon molecular structure. Functional groups were characterized using X-ray photoelectron spectroscopy, acid/base titrations, temperature-programmed desorption, and Fourier transform infrared spectroscopy. The influence of carbon structure, porosity, and surface functional groups on the redox reactions of vanadium was investigated using cyclic voltammetry and electrical impedance spectroscopy. The VO2+/VO2 + and V2+/V3+ couples had well-defined peaks in cyclic voltammetry, with the former being the most intense, but the V3+/VO2+ couple was not observed for samples carbonized under nitrogen. The results show that V2+/V3+ and VO2+/VO2 + couples observed in cyclic voltammograms were enhanced for carbonization temperatures up to 800 °C. Electrical impedance spectroscopy also showed impedance trends. The electrochemistry results are primarily related to changes in carbon structure and the catalysis of V3+ oxidation by surface functional groups in the carbon structure. The V3+/VO2+ couple was limited by slow kinetics, but it occurs on specific oxygen and nitrogen sites in the carbon structure. The oxidation of V(iii) to V(iv) only occurs on a limited number of surface sites, and the outer-sphere electron transfer to oxidize V(iii) takes place at much more positive potentials. The coulombic, voltage, and energy efficiency of the carbon electrodes were suitable for batteries.