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@ARTICLE{Nong:858727,
author = {Nong, Hong Nhan and Reier, Tobias and Oh, Hyung-Suk and
Gliech, Manuel and Paciok, Paul and Vu, Thu Ha Thi and
Teschner, Detre and Heggen, Marc and Petkov, Valeri and
Schlögl, Robert and Jones, Travis and Strasser, Peter},
title = {{A} unique oxygen ligand environment facilitates water
oxidation in hole-doped {I}r{N}i{O}x core–shell
electrocatalysts},
journal = {Nature catalysis},
volume = {1},
number = {11},
issn = {2520-1158},
address = {[London]},
publisher = {Macmillan Publishers Limited, part of Springer Nature},
reportid = {FZJ-2018-07572},
pages = {841 - 851},
year = {2018},
abstract = {The electro-oxidation of water to oxygen is expected to
play a major role in the development of future
electrochemical energy conversion and storage technologies.
However, the slow rate of the oxygen evolution reaction
remains a key challenge that requires fundamental
understanding to facilitate the design of more active and
stable electrocatalysts. Here, we probe the local geometric
ligand environment and electronic metal states of
oxygen-coordinated iridium centres in nickel-leached
IrNi@IrOx metal oxide core–shell nanoparticles under
catalytic oxygen evolution conditions using operando X-ray
absorption spectroscopy, resonant high-energy X-ray
diffraction and differential atomic pair correlation
analysis. Nickel leaching during catalyst activation
generates lattice vacancies, which in turn produce uniquely
shortened Ir–O metal ligand bonds and an unusually large
number of d-band holes in the iridium oxide shell. Density
functional theory calculations show that this increase in
the formal iridium oxidation state drives the formation of
holes on the oxygen ligands in direct proximity to lattice
vacancies. We argue that their electrophilic character
renders these oxygen ligands susceptible to nucleophilic
acid–base-type O–O bond formation at reduced kinetic
barriers, resulting in strongly enhanced reactivities.},
cin = {PGI-5},
ddc = {540},
cid = {I:(DE-Juel1)PGI-5-20110106},
pnm = {143 - Controlling Configuration-Based Phenomena (POF3-143)},
pid = {G:(DE-HGF)POF3-143},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000449799200011},
doi = {10.1038/s41929-018-0153-y},
url = {https://juser.fz-juelich.de/record/858727},
}