Operando XAFS on Hydrated Calcium Vanadium Bronze Cathode for Aqueous Zn-ion Storage

Multivalent ion storage and aqueous electrochemical systems continue to build interest for energy application. The Zn-ion system with 2 electron transfer and an ideal metal anode is a strong candidate but is still at the early stage of development. Using both in situ near-edge (XANES) and X-ray absorption fine structure spectroscopy, EXAFS, a nanostructured cathode material, Ca_xV₂O₅-H₂O (CVO), was probed at the V-K absorption edge. This operando study reveals the local electronic and geometric structure changes for CVO during galvanostatic cycling as the active material in an aqueous Zn-ion cell. The XANES data provides a fine resolution to track the evolution of the vanadium oxidative state and near-neighbor coordination sphere showing subtle shifts and delocalized charge. The Zn-ion influence on the V-K absorption edge is visualized using a difference technique called Δμ. Coupled with theoretical calculations and modelling, the extended region extracted local bonding information further confirms excellent electronic and structural reversibility of this vanadium oxide bronze in an aqueous Zn-ion electrochemical cell.     

The enormity of the zinc deficiency problem and available solutions; an overview

The societal cost of micronutrient deficiency (MND) or the “hidden hunger” is in millions of dollars/year, reducing the GDP of some countries by as much as 11%. Zn is an important micronutrient for both plants and animals. An estimated 17% of the world population, or around 1.1 billion people, are at the risk of zinc (Zn) deficiency. The deficiency has been related to adverse pregnancy outcomes, stunted growth, premature deaths, immune system dysfunctions, neuro-behavioral disorders, and recently with the failure to recover from COVID-19. These health risks associated with Zn deficiency have compelled FAO and WHO to recommend Zn fortification of diet. Correcting Zn deficiency is a challenge due to several reasons. Close to half of the agricultural soils are Zn deficient, and chemical Zn fertilizers are costly and ineffective. Developing Zn-rich crops through plant breeding and genetic engineering is challenging. Zn-dense diet is costly and cannot be implemented in the low-income region most affected by Zn deficiency. Lack of consensus among regulatory bodies on defining and diagnosing Zn deficiency in plants and Humans. Awareness and other sociocultural issues. Among the most important available solutions are zinc biofortification of the cereal crops, use of zinc biofertilizers, development of Zn-efficient crops with reduced phytate content. The use of Zn supplements, dietary modification, and diversification, especially with fish, are proposed as the most accessible and affordable solutions. Awareness programs in areas suffering the most from Zn deficiency are required. Despite the suggestions from FAO and WHO, global efforts to combat Zn deficiency matching those for combating diseases like HIV are not in place. Coordinated efforts of the international community, especially policy-makers, agricultural scientists, dieticians, physicians, and others, are required to address the issue of hidden hunger.     

Pitfalls in X-ray absorption spectroscopy analysis and interpretation: A practical guide for general users

Despite the growing popularity of X-ray absorption spectroscopy (XAS) in scientific research, many researchers do not receive formalized training on this technique. Some of them learned from online resources, which only briefly introduce XAS and its applications. Here, this article aims to provide the overview of tips about the XAS analysis, general rules, as well as required information for presenting XAS data in publications, and some common mistakes in XAS data interpretations. Armed with these basics, the motivated aspiring XAS researchers will find existing resources more accessible and can progress much faster in understanding and using XAS.     

The Effect of the Side Chain on Gelation Properties of Bile Acid Alkyl Amides

Six bile acid alkyl amide derivatives were studied with respect to their gelation properties. The derivatives were composed of three different bile acids with hexyl or cyclohexyl side chains. The gelation behaviour of all six compounds were studied for 36 solvents with varying polarities. Gelation was observed mainly in aromatic solvents, which is characteristic for bile-acid-based low molecular weight gelators. Out of 108 bile acid-solvent combinations, a total of 44 gel systems were formed, 28 of which from lithocholic acid derivatives, only two from deoxycholic acid derivatives, and 14 from cholic acid derivatives. The majority of the gel systems were formed from bile acids with hexyl side chains, contrary to the cyclohexyl group, which seems to be a poor gelation moiety. These results indicate that the spatial demand of the side chain is the key feature for the gelation properties of the bile acid amides.     

Planar Iron Hydride Nanoclusters: Combined Spectroscopic and Theoretical Insights into Structures and Building Principles

The controlled assembly of well-defined planar nanoclusters from molecular precursors is synthetically challenging and often plagued by the predominant formation of 3D-structures and nanoparticles. Herein, we report planar iron hydride nanoclusters from reactions of main group element hydrides with iron(II) bis(hexamethyldisilazide). The structures and properties of isolated Fe₄, Fe₆, and Fe₇ nanoplatelets and calculated intermediates enable an unprecedented insight into the underlying building principle and growth mechanism of iron clusters, metal monolayers, and nanoparticles.     

The first representative of a new class of charge transfer complexes in o-quinone series for organic semiconductors

The first representative of a new class of charge transfer complexes for organic semiconductors was synthesized. The reaction of p-nitroaniline (PNA) with [1,10]-phenanthroline-5,6-dione (PD) results in the formation of a stable molecular charge transfer (CT) complex PNA₃-PD₂ in a ratio of 3:2. The structure of the molecular CT complex PNA₃-PD₂ was established by X-ray diffraction studies. Using the density functional theory method, it is shown that several types of intermolecular interactions are realized in the complex: between the PNA amino group and the nitro group of another PNA molecule, carbonyl groups, and PD nitrogen atoms. Complex PNA₃-PD₂ is stable only in solid form. The diffuse reflectance UV–vis spectrum of PNA₃-PD₂ crystal powder is characterized by the intense weakly structured long-wavelength absorption band up to 650 nm. Quantum chemical calculations of the electronic structure have shown that the complex PNA₃-PD₂ is a straight-band semiconductor with a band gap of 2.11 eV.     

Synthesis of 1-(2-Fluorophenyl)pyrazoles by 1,3-Dipolar Cycloaddition of the Corresponding Sydnones

3-Arylsydnones bearing fluorine and bromine atoms on the benzene ring were synthesized from N-nitroso-2-fluorophenylglycines and characterized by NMR spectroscopy. These were employed further in synthesis of the corresponding 1-(2-fluorophenyl)pyrazoles by 1,3-dipolar cycloaddition reaction with dimethyl acetylenedicarboxylate (DMAD) as activated dipolarophile. The sydnones as reaction intermediates were characterized by single crystal X-ray diffraction analysis showing interesting features such as halogen bonding as an important interaction in modeling the crystal structure.     

Computational Study of the Electron Spectra of Vapor-Phase Indole and Four Azaindoles

After geometry optimization, the electron spectra of indole and four azaindoles are calculated by density functional theory. Available experimental photoemission and excitation data for indole and 7-azaindole are used to compare with the theoretical values. The results for the other azaindoles are presented as predictions to help the interpretation of experimental spectra when they become available.     

Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering

Application of low-cost carbon black from lignin highly depends on the materials properties, which might by determined by raw material and processing conditions. Four different technical lignins were subjected to thermostabilization followed by stepwise heat treatment up to a temperature of 2000 °C in order to obtain micro-sized carbon particles. The development of the pore structure, graphitization and inner surfaces were investigated by X-ray scattering complemented by scanning electron microscopy and FTIR spectroscopy. Lignosulfonate-based carbons exhibit a complex pore structure with nanopores and mesopores that evolve by heat treatment. Organosolv, kraft and soda lignin-based samples exhibit distinct pores growing steadily with heat treatment temperature. All carbons exhibit increasing pore size of about 0.5–2 nm and increasing inner surface, with a strong increase between 1200 °C and 1600 °C. The chemistry and bonding nature shifts from basic organic material towards pure graphite. The crystallite size was found to increase with the increasing degree of graphitization. Heat treatment of just 1600 °C might be sufficient for many applications, allowing to reduce production energy while maintaining materials properties.