Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K

Production of metallic iron through molten oxide electrolysis using inert electrodes is an alternative route for fast ironmaking without CO2 emissions. The fact that many inorganic oxides melt at ultrahigh temperatures (>1500 K) challenges conventional electro-analytical techniques used in aqueous, organic and molten salt electrolytes. However, in order to design a feasible and effective electrolytic process, it is necessary to best understand the electrochemical properties of iron ions in molten oxide electrolytes. In this work, a magnesia-stabilised zirconia (MSZ) tube with a closed end was used to construct an integrated three-electrode cell with the “MSZ | Pt | O2 (air)” assembly functioning as the solid electrolyte, the reference electrode and also the counter electrode. Electrochemical reduction of iron ions was systematically investigated on an iridium (Ir) wire working electrode in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K by cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and potentiostatic electrolysis (PE). The results show that the electro-reduction of the Fe2+ ion to Fe on the Ir electrode in the molten slag follows a single two-electron transfer step, and the rate of the process is diffusion controlled. The peak current on the obtained CVs is proportional to the concentration of the Fe2+ ion in the molten slag and the square root of scan rate. The diffusion coefficient of Fe2+ ions in the molten slag containing 5 wt% FeO at 1723 K was derived to be (3.43 ± 0.06)×10-6 cm2 s-1 from CP analysis. However, a couple of following processes, i.e. alloy formation on the Ir electrode surface and interdiffusion were found to affect the kinetics of iron deposition. An ECC mechanism is proposed to account for the CV observations. The findings from this work confirm that zirconia-based solid electrolytes can play an important role in electrochemical fundamental research in high temperature molten slag electrolytes

Yttria-stabilized zirconia aided electrochemical investigation on ferric ions in mixed molten calcium and sodium chlorides

Electrolytic reduction of dissolved iron oxide to metal iron in molten salts with an inert anode is an alternative short route for steelmaking without CO2 emissions. A novel and simple integrated yttria-stabilized zirconia (YSZ) cell was constructed from a YSZ tube with a closed end. The YSZ tube played multiple functions, including the container for the molten salts, the solid electrolyte membrane in the O2−|YSZ|Pt|O2 (air) reference electrode (RE), and the solid electrolyte membrane between the working and counter electrodes (WE and CE). Electrochemical behavior of ferric ions (Fe3+) that were formed by dissolution of 0.5 wt pct Fe2O3 in the molten CaCl2-NaCl eutectic mixture was investigated on a Pt WE at 1273 K by various electrochemical techniques including cyclic voltammetry, linear scan voltammetry, square wave voltammetry, chronopotentiometry, chronoamperometry, and potentiostatic electrolysis. Analysis of the mechanism of electrode reactions was further assisted by scanning electron microscopy, energy dispersive X-ray spectroscopy, and X-ray diffraction. Some electrochemical parameters were obtained, including the number of exchanged electrons and the diffusion coefficient of ferric ions in the mixed molten salts. The results from various electrochemical techniques are in good agreement with each other, and show that the electrochemical reduction of Fe3+ to Fe in the molten salt mixture could be a single three-electron transfer step and diffusion-controlled reaction that was also possibly reversible. This work may form the foundation for extraction of iron and alloys from molten salts and also provide a stable O2−|YSZ|Pt|O2 (air) RE with wide applicability for investigation on electrochemical properties of other electroactive metal oxides in molten salts

Deconvolution of single-cell multi-omics layers reveals regulatory heterogeneity

Heterogeneity in gene expression and epigenetic states exists across individual cells. Here, the authors develop scCAT-seq, a technique for simultaneously performing ATAC-seq and RNA-seq within the same single cell

Wetting and interfacial interaction of molten iron on MgO substrate under different oxygen partial pressures

The interaction between molten iron and refractory is of great significance to understand the damage of refractory in steelmaking processes. In this work, the interactions between the molten iron and three kinds of magnesia aggregates: No. 1 containing CaZrO3-ZrO2 intergranular phase (mainly CaZrO3), No. 2 containing ZrO2-MgAl2O4 intergranular phase (mainly ZrO2) and No. 3 fused magnesia, were studied by the sessile drop method at 1823 K under two kinds of oxygen partial pressures of PO2 ≈ 1.87 × 10−1 Pa and PO2 ≈ 1.87 × 10−3 Pa. It was found that the interaction mechanism between molten iron and substrate was almost the same under the two oxygen partial pressures. No. 2 substrate had a larger interacted area with molten iron due to its physical properties and chemical composition and more amount of slag was formed between them. The oxygen was easy to be released from the closed pores in No. 2 substrate so that the molten iron on No. 2 substrate had higher oxygen content, resulting in the decreases of the contact angle and the surface tension of molten iron. Accordingly, No. 2 substrate was penetrated most seriously. The intergranular phase of No. 1 substrate was more resistant to FeO corrosion than that of No. 2 substrate. The FeO penetration into No. 3 substrate was mainly along the grain boundary. The larger bulk density and grain size of No. 3 substrate could reduce the FeO penetration

Lake-centred sedentary lifestyle of early Tibetan Plateau Indigenous populations at high elevation 4,400 years ago

The onset of sedentism on the Tibetan Plateau is often presumed to be associated with the dispersal of agriculture or farmers from archaeological sites located in the low elevation margins of the plateau. Previous studies of the plateau assumed that all foragers were probably mobile, but few systematic excavations at forager sites have been conducted to inform us about their settlement patterns. Here we report the world’s highest elevation sedentary way of living exhibited by the Mabu Co site at 4,446 metres above sea level, deep in the interior of the Tibetan Plateau 4,400–4,000 years ago. Our interdisciplinary study indicates that the site was occupied by Indigenous inhabitants of the plateau, representing the earliest known DNA evidence of foragers who predominantly harbour the southern plateau ancestry. The evidence shows that they had a sedentary lifestyle primarily supported by fishing at nearby lakes, supplemented by mammal and bird hunting, as well as small-scale exchanges of millet and rice crops