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
AN - SCOPUS:85041119828
VL - 61
SP - 267
EP - 275
JO - Topics in Catalysis
JF - Topics in Catalysis
SN - 1022-5528
IS - 3-4
ER -