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 aqueou...

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Main Authors: Gao, Yunming, Yang, Chuanghuang, Zhang, Canlei, Qin, Qingwei, Chen, George Z.
Format: Article
Published: Royal Society of Chemistry 2017
Online Access:https://eprints.nottingham.ac.uk/43421/
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author Gao, Yunming
Yang, Chuanghuang
Zhang, Canlei
Qin, Qingwei
Chen, George Z.
author_facet Gao, Yunming
Yang, Chuanghuang
Zhang, Canlei
Qin, Qingwei
Chen, George Z.
author_sort Gao, Yunming
building Nottingham Research Data Repository
collection Online Access
description 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.
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spelling nottingham-434212020-05-04T18:52:14Z https://eprints.nottingham.ac.uk/43421/ Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K Gao, Yunming Yang, Chuanghuang Zhang, Canlei Qin, Qingwei Chen, George Z. 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. Royal Society of Chemistry 2017-06-28 Article PeerReviewed Gao, Yunming, Yang, Chuanghuang, Zhang, Canlei, Qin, Qingwei and Chen, George Z. (2017) Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K. Physical Chemistry Chemical Physics, 24 (19). pp. 15876-15890. ISSN 1463-9084 http://pubs.rsc.org/en/Content/ArticleLanding/2017/CP/C7CP01945A#!divAbstract doi:10.1039/C7CP01945A doi:10.1039/C7CP01945A
spellingShingle Gao, Yunming
Yang, Chuanghuang
Zhang, Canlei
Qin, Qingwei
Chen, George Z.
Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K
title Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K
title_full Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K
title_fullStr Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K
title_full_unstemmed Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K
title_short Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the SiO2-CaO-MgO-Al2O3 molten slag at 1723 K
title_sort magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in the sio2-cao-mgo-al2o3 molten slag at 1723 k
url https://eprints.nottingham.ac.uk/43421/
https://eprints.nottingham.ac.uk/43421/
https://eprints.nottingham.ac.uk/43421/