Electronic Structure of IrO2: The Role of the Metal d Orbitals

Ping, Yuan; Galli, Giulia; Goddard, William A.

doi:10.1021/acs.jpcc.5b00861

Electronic Structure of IrO₂: The Role of the Metal d Orbitals

Journal Article · Thu Apr 23 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.5b00861· OSTI ID:1467645

Ping, Yuan ^[1]; Galli, Giulia ^[2]; Goddard, William A. ^[3]

California Inst. of Technology (CalTech), Pasadena, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); California Institute of Technology
Univ. of Chicago, IL (United States)
California Inst. of Technology (CalTech), Pasadena, CA (United States)

IrO₂ is one of the most active catalysts for the oxygen evolution reaction (OER) and remains the only known stable OER catalyst in acidic conditions. As a first step in understanding the mechanism for OER we carried out detailed Density Functional Theory (DFT) studies of the electronic structure of IrO₂. We compared the electronic states and magnetic properties of IrO₂ using several density functionals. We found that DFT with hybrid functionals (B3PW and PBE0) leads to a weak ferromagnetic coupling, although IrO₂ has often been reported as nonmagnetic. We also found a magnetic ground state for RuO₂, whose electronic structure is similar to that of IrO₂. Ru–Ru antiferromagnetic interaction has been observed experimentally in nanoparticle RuO₂. Further low temperature measurements are necessary to confirm whether a weak magnetism may occur below 20 K in IrO₂. We also found that PBE leads to a better agreement with the experimental XPS spectra, compared with hybrid functionals and PBE+U.

View Accepted Manuscript (DOE)

Research Organization:: California Inst. of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0004993

OSTI ID:: 1467645

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 21 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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