Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2

Limited selectivity in coexisted anodic reactions on lead-based anodes leads to severe lead-dissolution, anodic slime-generation and high energy-consumption. Herein, anodic reaction selectivity was regulated by phase-controlled MnO2 (MnO2-PC) on lead-based anodes which was prepared under a lower vol...

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Main Authors: Zhuang, Siwei, Duan, Ning, Jiang, Linhua, Zhang, Feilong, Hu, Jun, Chen, Zhong, Xu, Fuyuan
Other Authors: School of Materials Science and Engineering
Format: Article
Language:English
Published: 2024
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Online Access:https://hdl.handle.net/10356/174071
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Institution: Nanyang Technological University
Language: English
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spelling sg-ntu-dr.10356-1740712024-03-13T08:46:03Z Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2 Zhuang, Siwei Duan, Ning Jiang, Linhua Zhang, Feilong Hu, Jun Chen, Zhong Xu, Fuyuan School of Materials Science and Engineering Engineering Lead-based anode Hazardous lead-containing slime Limited selectivity in coexisted anodic reactions on lead-based anodes leads to severe lead-dissolution, anodic slime-generation and high energy-consumption. Herein, anodic reaction selectivity was regulated by phase-controlled MnO2 (MnO2-PC) on lead-based anodes which was prepared under a lower voltage and a higher Mn2+ concentration. Compared with α-MnO2 formed under normal conditions, composite phase of γ-MnO2 and ε-MnO2 was obtained from MnO2-PC with specific crystal planes exposure and rich oxygen vacancy defects enabling higher oxygen evolution reaction selectivity (OER, overpotential reduced by ∼99 mV). Meanwhile, reaction of lead corrosion and manganese oxidation, as the main reasons for generation of hazardous lead-containing slime, were synergistically suppressed by 86.8% and 91.7%, respectively. Density functional theory (DFT) calculations further clarified that the change in coordinative environment of Mn and O brought lower energy barrier of rate-determining step of OER and stronger electron delocalization ability of MnO2, beneficial for promoting the catalysis of OER. MnO2-PC also displayed excellent inhibition effects on the generation and accumulation of Mn3+, an important precursor of MnO2 slime, and changed the selectivity in the oxidative path of Mn2+. The long-term electrolysis tests proved the stable performance of Pb–Ag/MnO2-PC. This study provides an efficient, low-cost, high economic benefits and environmental-friendly strategy for designing target functional materials towards reaction selectivity regulation via phase-control and microstructure reconstruction. This research was supported by the National Natural Science Foundation of China (52174385; 41877392), and Fundamental Research Funds for the Central Universities, Tongji University (22120220166). 2024-03-13T08:45:17Z 2024-03-13T08:45:17Z 2023 Journal Article Zhuang, S., Duan, N., Jiang, L., Zhang, F., Hu, J., Chen, Z. & Xu, F. (2023). Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2. Journal of Cleaner Production, 404, 136961-. https://dx.doi.org/10.1016/j.jclepro.2023.136961 0959-6526 https://hdl.handle.net/10356/174071 10.1016/j.jclepro.2023.136961 2-s2.0-85151005953 404 136961 en Journal of Cleaner Production © 2023 Elsevier Ltd. All rights reserved.
institution Nanyang Technological University
building NTU Library
continent Asia
country Singapore
Singapore
content_provider NTU Library
collection DR-NTU
language English
topic Engineering
Lead-based anode
Hazardous lead-containing slime
spellingShingle Engineering
Lead-based anode
Hazardous lead-containing slime
Zhuang, Siwei
Duan, Ning
Jiang, Linhua
Zhang, Feilong
Hu, Jun
Chen, Zhong
Xu, Fuyuan
Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2
description Limited selectivity in coexisted anodic reactions on lead-based anodes leads to severe lead-dissolution, anodic slime-generation and high energy-consumption. Herein, anodic reaction selectivity was regulated by phase-controlled MnO2 (MnO2-PC) on lead-based anodes which was prepared under a lower voltage and a higher Mn2+ concentration. Compared with α-MnO2 formed under normal conditions, composite phase of γ-MnO2 and ε-MnO2 was obtained from MnO2-PC with specific crystal planes exposure and rich oxygen vacancy defects enabling higher oxygen evolution reaction selectivity (OER, overpotential reduced by ∼99 mV). Meanwhile, reaction of lead corrosion and manganese oxidation, as the main reasons for generation of hazardous lead-containing slime, were synergistically suppressed by 86.8% and 91.7%, respectively. Density functional theory (DFT) calculations further clarified that the change in coordinative environment of Mn and O brought lower energy barrier of rate-determining step of OER and stronger electron delocalization ability of MnO2, beneficial for promoting the catalysis of OER. MnO2-PC also displayed excellent inhibition effects on the generation and accumulation of Mn3+, an important precursor of MnO2 slime, and changed the selectivity in the oxidative path of Mn2+. The long-term electrolysis tests proved the stable performance of Pb–Ag/MnO2-PC. This study provides an efficient, low-cost, high economic benefits and environmental-friendly strategy for designing target functional materials towards reaction selectivity regulation via phase-control and microstructure reconstruction.
author2 School of Materials Science and Engineering
author_facet School of Materials Science and Engineering
Zhuang, Siwei
Duan, Ning
Jiang, Linhua
Zhang, Feilong
Hu, Jun
Chen, Zhong
Xu, Fuyuan
format Article
author Zhuang, Siwei
Duan, Ning
Jiang, Linhua
Zhang, Feilong
Hu, Jun
Chen, Zhong
Xu, Fuyuan
author_sort Zhuang, Siwei
title Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2
title_short Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2
title_full Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2
title_fullStr Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2
title_full_unstemmed Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2
title_sort reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: driving mechanism of pb-based anode with oxygen vacancy-rich mno2
publishDate 2024
url https://hdl.handle.net/10356/174071
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