Super-exchange interaction induced overall optimization in ferromagnetic perovskite oxides enables ultrafast water oxidation

Jie Dai, Yinlong Zhu, Yichun Yin, Hassan A. Tahini, Daqin Guan, Feifei Dong, Qian Lu, Sean C. Smith, Xiwang Zhang, Huanting Wang, Wei Zhou, Zongping Shao

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super-exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition-dependent OER activity in SrCo1 x Rux O3− δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super-exchange interaction between high spin (HS) Co3+ and Ru5+ ions. Induced by the unique Co3+–O–Ru5+ super-exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co3+/Co4+, Ru5+, and O2 2−/O, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm−2, which exceeds the benchmark RuO2 and most well-known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.

Original languageEnglish
Article number1903120
Number of pages11
JournalSmall
DOIs
Publication statusAccepted/In press - 12 Aug 2019

Keywords

  • active sites
  • electrical conductivity
  • ferromagnetic perovskite oxides
  • super-exchange effect
  • water oxidation

Cite this

Dai, Jie ; Zhu, Yinlong ; Yin, Yichun ; Tahini, Hassan A. ; Guan, Daqin ; Dong, Feifei ; Lu, Qian ; Smith, Sean C. ; Zhang, Xiwang ; Wang, Huanting ; Zhou, Wei ; Shao, Zongping. / Super-exchange interaction induced overall optimization in ferromagnetic perovskite oxides enables ultrafast water oxidation. In: Small. 2019.
@article{e23125b394ff4eb199562db55e977fa1,
title = "Super-exchange interaction induced overall optimization in ferromagnetic perovskite oxides enables ultrafast water oxidation",
abstract = "Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super-exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition-dependent OER activity in SrCo1 x Rux O3− δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super-exchange interaction between high spin (HS) Co3+ and Ru5+ ions. Induced by the unique Co3+–O–Ru5+ super-exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co3+/Co4+, Ru5+, and O2 2−/O−, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm−2, which exceeds the benchmark RuO2 and most well-known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.",
keywords = "active sites, electrical conductivity, ferromagnetic perovskite oxides, super-exchange effect, water oxidation",
author = "Jie Dai and Yinlong Zhu and Yichun Yin and Tahini, {Hassan A.} and Daqin Guan and Feifei Dong and Qian Lu and Smith, {Sean C.} and Xiwang Zhang and Huanting Wang and Wei Zhou and Zongping Shao",
year = "2019",
month = "8",
day = "12",
doi = "10.1002/smll.201903120",
language = "English",
journal = "Small",
issn = "1613-6810",
publisher = "Wiley-Blackwell",

}

Super-exchange interaction induced overall optimization in ferromagnetic perovskite oxides enables ultrafast water oxidation. / Dai, Jie; Zhu, Yinlong; Yin, Yichun; Tahini, Hassan A.; Guan, Daqin; Dong, Feifei; Lu, Qian; Smith, Sean C.; Zhang, Xiwang; Wang, Huanting; Zhou, Wei; Shao, Zongping.

In: Small, 12.08.2019.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Super-exchange interaction induced overall optimization in ferromagnetic perovskite oxides enables ultrafast water oxidation

AU - Dai, Jie

AU - Zhu, Yinlong

AU - Yin, Yichun

AU - Tahini, Hassan A.

AU - Guan, Daqin

AU - Dong, Feifei

AU - Lu, Qian

AU - Smith, Sean C.

AU - Zhang, Xiwang

AU - Wang, Huanting

AU - Zhou, Wei

AU - Shao, Zongping

PY - 2019/8/12

Y1 - 2019/8/12

N2 - Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super-exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition-dependent OER activity in SrCo1 x Rux O3− δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super-exchange interaction between high spin (HS) Co3+ and Ru5+ ions. Induced by the unique Co3+–O–Ru5+ super-exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co3+/Co4+, Ru5+, and O2 2−/O−, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm−2, which exceeds the benchmark RuO2 and most well-known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.

AB - Oxygen evolution reaction (OER) is crucial in many renewable electrochemical technologies including regenerative fuel cells, rechargeable metal–air batteries, and water splitting. It is found that abundant active sites with favorable electronic structure and high electrical conductivity play a dominant role in achieving high electrocatalytic efficiency of perovskites, thus efficient strategies need to be designed to generate multiple beneficial factors for OER. Here, highlighted is an unusual super-exchange effect in ferromagnetic perovskite oxide to optimize active sites and enhance electrical conductivity. A systematic exploration about the composition-dependent OER activity in SrCo1 x Rux O3− δ (denoted as SCRx) (x = 0.0–1.0) perovskite is displayed with special attention on the role of super-exchange interaction between high spin (HS) Co3+ and Ru5+ ions. Induced by the unique Co3+–O–Ru5+ super-exchange interactions, the SCR0.1 is endowed with abundant OER active species including Co3+/Co4+, Ru5+, and O2 2−/O−, high electrical conductivity, and metal–oxygen covalency. Benefiting from these advantageous factors for OER electrocatalysis, the optimized SCR0.1 catalyst exhibits a remarkable activity with a low overpotential of 360 mV at 10 mA cm−2, which exceeds the benchmark RuO2 and most well-known perovskite oxides reported so far, while maintaining excellent durability. This work provides a new pathway in developing perovskite catalysts for efficient catalysis.

KW - active sites

KW - electrical conductivity

KW - ferromagnetic perovskite oxides

KW - super-exchange effect

KW - water oxidation

UR - http://www.scopus.com/inward/record.url?scp=85070722550&partnerID=8YFLogxK

U2 - 10.1002/smll.201903120

DO - 10.1002/smll.201903120

M3 - Article

JO - Small

JF - Small

SN - 1613-6810

M1 - 1903120

ER -