Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis
Bixbyite $$\alpha $$-Mn2O3 is an inexpensive Earth-abundant mineral that can be used to drive both oxygen evolution (OER) and oxygen reduction reactions (ORR) in alkaline conditions. It possesses a subtle orthorhombic $$ \to $$ cubic phase change near room temperature that suppresses Jahn–Teller dis...
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doaj-91ee15f3b0bf4250940f3006e65e6d822021-04-21T16:14:24ZengTaylor & Francis GroupScience and Technology of Advanced Materials1468-69961878-55142021-12-0122114114910.1080/14686996.2020.18689491868949Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysisJunais Habeeb Mokkath0Maryam Jahan1Masahiko Tanaka2Satoshi Tominaka3Joel Henzie4National Institute for Materials Science (NIMS)National Institute for Materials Science (NIMS)National Institute for Materials ScienceNational Institute for Materials Science (NIMS)National Institute for Materials Science (NIMS)Bixbyite $$\alpha $$-Mn2O3 is an inexpensive Earth-abundant mineral that can be used to drive both oxygen evolution (OER) and oxygen reduction reactions (ORR) in alkaline conditions. It possesses a subtle orthorhombic $$ \to $$ cubic phase change near room temperature that suppresses Jahn–Teller distortions and presents a unique opportunity to study how atomic structure affects the electronic structure and catalytic activity at a temperature range that is easily accessible in OER/ORR experiments. Previously, we observed that heat-treated $$\alpha $$-Mn2O3 had a better performance as a bifunctional catalyst in the oxygen evolution (OER) and oxygen reduction reactions (ORR) (Dalton Trans. 2016, 45, 18,494–18,501). We hypothesized that heat-treatment pinned the material into a more electrochemically active cubic phase. In this manuscript, we use high-resolution X-ray diffraction to collect the temperature-dependent structures of $$\alpha $$-Mn2O3, and then input them into ab initio calculations. The electronic structure calculations indicate that the orthorhombic $$ \to $$ cubic phase transition causes the Mn 3d and O 2p bands to overlap and mix covalently, transforming $$\alpha $$-Mn2O3 from a semiconductor to a semimetal. This subtle change in structure also modifies Mn-O-Mn bond distances, which may improve the activity of the material in oxygen electrochemistry. OER and ORR experiments were performed using the same electrode at various temperatures. They show a jump in the exchange current density near the phase change temperature, demonstrating the higher activity of the cubic phase.http://dx.doi.org/10.1080/14686996.2020.1868949manganese oxidejahn–teller distortionsphase changeoerorr |
collection |
DOAJ |
language |
English |
format |
Article |
sources |
DOAJ |
author |
Junais Habeeb Mokkath Maryam Jahan Masahiko Tanaka Satoshi Tominaka Joel Henzie |
spellingShingle |
Junais Habeeb Mokkath Maryam Jahan Masahiko Tanaka Satoshi Tominaka Joel Henzie Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis Science and Technology of Advanced Materials manganese oxide jahn–teller distortions phase change oer orr |
author_facet |
Junais Habeeb Mokkath Maryam Jahan Masahiko Tanaka Satoshi Tominaka Joel Henzie |
author_sort |
Junais Habeeb Mokkath |
title |
Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis |
title_short |
Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis |
title_full |
Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis |
title_fullStr |
Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis |
title_full_unstemmed |
Temperature-dependent electronic structure of bixbyite α-Mn2O3 and the importance of a subtle structural change on oxygen electrocatalysis |
title_sort |
temperature-dependent electronic structure of bixbyite α-mn2o3 and the importance of a subtle structural change on oxygen electrocatalysis |
publisher |
Taylor & Francis Group |
series |
Science and Technology of Advanced Materials |
issn |
1468-6996 1878-5514 |
publishDate |
2021-12-01 |
description |
Bixbyite $$\alpha $$-Mn2O3 is an inexpensive Earth-abundant mineral that can be used to drive both oxygen evolution (OER) and oxygen reduction reactions (ORR) in alkaline conditions. It possesses a subtle orthorhombic $$ \to $$ cubic phase change near room temperature that suppresses Jahn–Teller distortions and presents a unique opportunity to study how atomic structure affects the electronic structure and catalytic activity at a temperature range that is easily accessible in OER/ORR experiments. Previously, we observed that heat-treated $$\alpha $$-Mn2O3 had a better performance as a bifunctional catalyst in the oxygen evolution (OER) and oxygen reduction reactions (ORR) (Dalton Trans. 2016, 45, 18,494–18,501). We hypothesized that heat-treatment pinned the material into a more electrochemically active cubic phase. In this manuscript, we use high-resolution X-ray diffraction to collect the temperature-dependent structures of $$\alpha $$-Mn2O3, and then input them into ab initio calculations. The electronic structure calculations indicate that the orthorhombic $$ \to $$ cubic phase transition causes the Mn 3d and O 2p bands to overlap and mix covalently, transforming $$\alpha $$-Mn2O3 from a semiconductor to a semimetal. This subtle change in structure also modifies Mn-O-Mn bond distances, which may improve the activity of the material in oxygen electrochemistry. OER and ORR experiments were performed using the same electrode at various temperatures. They show a jump in the exchange current density near the phase change temperature, demonstrating the higher activity of the cubic phase. |
topic |
manganese oxide jahn–teller distortions phase change oer orr |
url |
http://dx.doi.org/10.1080/14686996.2020.1868949 |
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