An Effective Way to Improve Bifunctional Electrocatalyst Activity of Manganese Oxide via Control of Bond Competition

Bohyun Kang, Xiaoyan Jin, Seung Mi Oh, Sharad B. Patil, Min Gyu Kim, Sun Hee Kim, Seong Ju Hwang

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

A critical role of bond competition in tailoring Mn valence state and bifunctional electrocatalyst activity of manganese oxide is evidenced by the remarkable improvement of the electrocatalyst activity of & #x03B1;-MnO2 upon the partial substitution of electronegative Ru4+ ion. The replacement of Mn4+ ion with more electronegative Ru4+ one is quite effective in weakening adjacent (Mn−O) bonds in terms of bond competition, leading to the stabilization of Jahn-Teller active Mn3+ species, as well as in providing electrocatalytically active Ru sites. The resulting Ru-substituted & #x03B1;-Mn1−xRuxO2 nanowires show much higher electrocatalyst activities for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) than does the physical mixture of & #x03B1;-MnO2 and RuO2, indicating the main role of (Mn−O) bond covalency in the optimization of the bifunctional electrocatalyst activity of manganese oxide. The present study underscores that, like the previous strategy of structural disorder enhancement, the substitution of highly electronegative cation can provide a novel efficient way of improving the electrocatalyst performance of manganese oxide via the bond competition between adjacent (Ru−O) and (Mn−O) bonds.

Original languageEnglish
Pages (from-to)107-116
Number of pages10
JournalApplied Catalysis B: Environmental
Volume236
DOIs
Publication statusPublished - 2018 Nov 15

Fingerprint

Manganese oxide
Electrocatalysts
manganese oxide
substitution
oxygen
ion
Substitution reactions
Ions
Oxygen
stabilization
replacement
cation
Nanowires
Cations
Stabilization
Positive ions

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Environmental Science(all)
  • Process Chemistry and Technology

Cite this

Kang, Bohyun ; Jin, Xiaoyan ; Oh, Seung Mi ; Patil, Sharad B. ; Kim, Min Gyu ; Kim, Sun Hee ; Hwang, Seong Ju. / An Effective Way to Improve Bifunctional Electrocatalyst Activity of Manganese Oxide via Control of Bond Competition. In: Applied Catalysis B: Environmental. 2018 ; Vol. 236. pp. 107-116.
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An Effective Way to Improve Bifunctional Electrocatalyst Activity of Manganese Oxide via Control of Bond Competition. / Kang, Bohyun; Jin, Xiaoyan; Oh, Seung Mi; Patil, Sharad B.; Kim, Min Gyu; Kim, Sun Hee; Hwang, Seong Ju.

In: Applied Catalysis B: Environmental, Vol. 236, 15.11.2018, p. 107-116.

Research output: Contribution to journalArticle

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AB - A critical role of bond competition in tailoring Mn valence state and bifunctional electrocatalyst activity of manganese oxide is evidenced by the remarkable improvement of the electrocatalyst activity of & #x03B1;-MnO2 upon the partial substitution of electronegative Ru4+ ion. The replacement of Mn4+ ion with more electronegative Ru4+ one is quite effective in weakening adjacent (Mn−O) bonds in terms of bond competition, leading to the stabilization of Jahn-Teller active Mn3+ species, as well as in providing electrocatalytically active Ru sites. The resulting Ru-substituted & #x03B1;-Mn1−xRuxO2 nanowires show much higher electrocatalyst activities for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) than does the physical mixture of & #x03B1;-MnO2 and RuO2, indicating the main role of (Mn−O) bond covalency in the optimization of the bifunctional electrocatalyst activity of manganese oxide. The present study underscores that, like the previous strategy of structural disorder enhancement, the substitution of highly electronegative cation can provide a novel efficient way of improving the electrocatalyst performance of manganese oxide via the bond competition between adjacent (Ru−O) and (Mn−O) bonds.

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