Orbital Physics of Perovskites for the Oxygen Evolution Reaction

Ryan Sharpe, Julen Munarriz, Tingbin Lim, Yunzhe Jiao, J. W. Niemantsverdriet, Victor Polo, Jose Gracia

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The study of magnetic perovskite oxides has led to novel and very active compounds for O2 generation and other energy applications. Focusing on three different case studies, we summarise the bulk electronic and magnetic properties that initially serve to classify active perovskite catalysts for the oxygen evolution reaction (OER). Ab-initio calculations centred on the orbital physics of the electrons in the d-shell provide a unique insight into the complex interplay between spin dependent interactions versus selectivity and OER reactivity that occurs in these transition-metal oxides. We analyse how the spin, orbital and lattice degrees of freedom establish rational design principles for OER. We observe that itinerant magnetism serves as an indicator for highly active oxygen electro-catalysts. Optimum active sites individually have a net magnetic moment, giving rise to exchange interactions which are collectively ferromagnetic, indicative of spin dependent transport. In particular, optimum active sites for OER need to possess sufficient empty orthogonal orbitals, oriented towards the ligands, to preserve an incoming spin aligned electron flow. Calculations from first principles open up the possibility of anticipating materials with improved electro-catalytic properties, based on orbital engineering.

Original languageEnglish
Pages (from-to)267-275
Number of pages9
JournalTopics in Catalysis
Volume61
Issue number3-4
Early online date29 Jan 2018
DOIs
Publication statusPublished - 1 Apr 2018

Keywords

  • Electrocatalysis
  • Exchange interactions
  • Orbital engineering
  • Orbital physics
  • Oxygen evolution reaction
  • Perovskites

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Sharpe, R., Munarriz, J., Lim, T., Jiao, Y., Niemantsverdriet, J. W., Polo, V., & Gracia, J. (2018). Orbital Physics of Perovskites for the Oxygen Evolution Reaction. Topics in Catalysis, 61(3-4), 267-275. https://doi.org/10.1007/s11244-018-0895-4

Orbital Physics of Perovskites for the Oxygen Evolution Reaction. / Sharpe, Ryan; Munarriz, Julen; Lim, Tingbin; Jiao, Yunzhe; Niemantsverdriet, J. W.; Polo, Victor; Gracia, Jose.

In: Topics in Catalysis, Vol. 61, No. 3-4, 01.04.2018, p. 267-275.

Research output: Contribution to journalArticle

Sharpe, R, Munarriz, J, Lim, T, Jiao, Y, Niemantsverdriet, JW, Polo, V & Gracia, J 2018, 'Orbital Physics of Perovskites for the Oxygen Evolution Reaction', Topics in Catalysis, vol. 61, no. 3-4, pp. 267-275. https://doi.org/10.1007/s11244-018-0895-4
Sharpe R, Munarriz J, Lim T, Jiao Y, Niemantsverdriet JW, Polo V et al. Orbital Physics of Perovskites for the Oxygen Evolution Reaction. Topics in Catalysis. 2018 Apr 1;61(3-4):267-275. https://doi.org/10.1007/s11244-018-0895-4
Sharpe, Ryan ; Munarriz, Julen ; Lim, Tingbin ; Jiao, Yunzhe ; Niemantsverdriet, J. W. ; Polo, Victor ; Gracia, Jose. / Orbital Physics of Perovskites for the Oxygen Evolution Reaction. In: Topics in Catalysis. 2018 ; Vol. 61, No. 3-4. pp. 267-275.
@article{3aaa107dec7e4019ab580c771eff9502,
title = "Orbital Physics of Perovskites for the Oxygen Evolution Reaction",
abstract = "The study of magnetic perovskite oxides has led to novel and very active compounds for O2 generation and other energy applications. Focusing on three different case studies, we summarise the bulk electronic and magnetic properties that initially serve to classify active perovskite catalysts for the oxygen evolution reaction (OER). Ab-initio calculations centred on the orbital physics of the electrons in the d-shell provide a unique insight into the complex interplay between spin dependent interactions versus selectivity and OER reactivity that occurs in these transition-metal oxides. We analyse how the spin, orbital and lattice degrees of freedom establish rational design principles for OER. We observe that itinerant magnetism serves as an indicator for highly active oxygen electro-catalysts. Optimum active sites individually have a net magnetic moment, giving rise to exchange interactions which are collectively ferromagnetic, indicative of spin dependent transport. In particular, optimum active sites for OER need to possess sufficient empty orthogonal orbitals, oriented towards the ligands, to preserve an incoming spin aligned electron flow. Calculations from first principles open up the possibility of anticipating materials with improved electro-catalytic properties, based on orbital engineering.",
keywords = "Electrocatalysis, Exchange interactions, Orbital engineering, Orbital physics, Oxygen evolution reaction, Perovskites",
author = "Ryan Sharpe and Julen Munarriz and Tingbin Lim and Yunzhe Jiao and Niemantsverdriet, {J. W.} and Victor Polo and Jose Gracia",
year = "2018",
month = "4",
day = "1",
doi = "10.1007/s11244-018-0895-4",
language = "English",
volume = "61",
pages = "267--275",
journal = "Topics in Catalysis",
issn = "1022-5528",
publisher = "Springer Netherlands",
number = "3-4",

}

TY - JOUR

T1 - Orbital Physics of Perovskites for the Oxygen Evolution Reaction

AU - Sharpe, Ryan

AU - Munarriz, Julen

AU - Lim, Tingbin

AU - Jiao, Yunzhe

AU - Niemantsverdriet, J. W.

AU - Polo, Victor

AU - Gracia, Jose

PY - 2018/4/1

Y1 - 2018/4/1

N2 - The study of magnetic perovskite oxides has led to novel and very active compounds for O2 generation and other energy applications. Focusing on three different case studies, we summarise the bulk electronic and magnetic properties that initially serve to classify active perovskite catalysts for the oxygen evolution reaction (OER). Ab-initio calculations centred on the orbital physics of the electrons in the d-shell provide a unique insight into the complex interplay between spin dependent interactions versus selectivity and OER reactivity that occurs in these transition-metal oxides. We analyse how the spin, orbital and lattice degrees of freedom establish rational design principles for OER. We observe that itinerant magnetism serves as an indicator for highly active oxygen electro-catalysts. Optimum active sites individually have a net magnetic moment, giving rise to exchange interactions which are collectively ferromagnetic, indicative of spin dependent transport. In particular, optimum active sites for OER need to possess sufficient empty orthogonal orbitals, oriented towards the ligands, to preserve an incoming spin aligned electron flow. Calculations from first principles open up the possibility of anticipating materials with improved electro-catalytic properties, based on orbital engineering.

AB - The study of magnetic perovskite oxides has led to novel and very active compounds for O2 generation and other energy applications. Focusing on three different case studies, we summarise the bulk electronic and magnetic properties that initially serve to classify active perovskite catalysts for the oxygen evolution reaction (OER). Ab-initio calculations centred on the orbital physics of the electrons in the d-shell provide a unique insight into the complex interplay between spin dependent interactions versus selectivity and OER reactivity that occurs in these transition-metal oxides. We analyse how the spin, orbital and lattice degrees of freedom establish rational design principles for OER. We observe that itinerant magnetism serves as an indicator for highly active oxygen electro-catalysts. Optimum active sites individually have a net magnetic moment, giving rise to exchange interactions which are collectively ferromagnetic, indicative of spin dependent transport. In particular, optimum active sites for OER need to possess sufficient empty orthogonal orbitals, oriented towards the ligands, to preserve an incoming spin aligned electron flow. Calculations from first principles open up the possibility of anticipating materials with improved electro-catalytic properties, based on orbital engineering.

KW - Electrocatalysis

KW - Exchange interactions

KW - Orbital engineering

KW - Orbital physics

KW - Oxygen evolution reaction

KW - Perovskites

UR - http://www.scopus.com/inward/record.url?scp=85041119828&partnerID=8YFLogxK

U2 - 10.1007/s11244-018-0895-4

DO - 10.1007/s11244-018-0895-4

M3 - Article

VL - 61

SP - 267

EP - 275

JO - Topics in Catalysis

JF - Topics in Catalysis

SN - 1022-5528

IS - 3-4

ER -