Electronic Structure of IrO<sub>2</sub>: The Role of the Metal d Orbitals

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

doi:10.1021/acs.jpcc.5b00861

Cited by 104 publications

(101 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Fig. 1(c) is magnified by a factor of ten to reveal the diversity of Ir 5d components near the Fermi level, which is key to most of its physical properties as well as chemical applications such as stable high-efficiency catalyst for water splitting [30].…”

Section: Methodsmentioning

confidence: 99%

Strong spin-orbit coupling and Dirac nodal lines in the three-dimensional electronic structure of metallic rutile IrO2

Jiang

Shi

et al. 2019

Phys. Rev. B

View full text Add to dashboard Cite

Using high-resolution angle-resolved photoemission spectroscopy and ab initio calculation, we have studied the bulk and surface electronic structure of metallic rutile 5d transition metal oxide IrO 2 that harbors both edge and corner sharing Ir-O octahedrons. We observe strong modulation of the band structure by spin-orbit coupling (SOC). The measured band structure is well reproduced by our ab initio calculation without band renormalization, suggesting the absence of the SOC-enhanced correlation effect in IrO 2. In accordance with the calculation, we visualize two types of Dirac nodal lines (DNLs) protected by mirror symmetry and nonsymmorphic crystal symmetry, respectively. SOC gaps the first type of DNLs, which may contribute largely to the strong spin Hall effect. The second type of DNLs at the edges of Brillouin zone, however, remain intact against SOC. Our results not only provide important insights into the exotic transport properties of IrO 2 , but also shed light on the understanding of the role of SOC in the iridate family.

show abstract

Section: Methodsmentioning

confidence: 99%

Strong spin-orbit coupling and Dirac nodal lines in the three-dimensional electronic structure of metallic rutile IrO2

Jiang

Shi

et al. 2019

Phys. Rev. B

View full text Add to dashboard Cite

show abstract

“…Next, we consider IrO 2 another rutile oxide, which is a highly active and the only known acid-stable catalyst for the oxygen evolution reaction (OER). 61,62 IrO 2 is metallic 63 and it is critical to understand the effect of solvation on its work function, since that determines the interfacial energetics and charge transfer between IrO 2 catalysts and semiconductor photoelectrodes. 64 We now apply our solvation protocol to estimate the work function shift for the most stable (110) surface 64 of IrO 2 .…”

Section: Iro 2 (110) Surfacementioning

confidence: 99%

Solvation effects on the band edge positions of photocatalysts from first principles

Ping

Sundararaman

Goddard

2015

Phys. Chem. Chem. Phys.

Self Cite

View full text Add to dashboard Cite

The band edge positions of photocatalysts relative to the redox potentials of water play an important role in determining the efficiency of photoelectrochemical cells. These band positions depend on the structure of the solid-liquid interface, but direct ab initio molecular dynamics calculations of these interfaces, while expected to be accurate, are too computationally demanding for high-throughput materials screening. Thus rapid theoretical screening of new photocatalyst materials requires simplified continuum solvation models that are suitable for treating solid-liquid interfaces. In this paper, we evaluate the accuracy of the recently developed CANDLE and SaLSA continuum solvation models for predicting solvation effects on the band positions of several well-studied surfaces [Si(111), TiO2(110), IrO2(110) and WO3(001)] in water. We find that the solvation effects vary considerably, ranging from <0.5 eV for hydrophobic surfaces, 0.5-1 eV for many hydrophilic oxide surfaces, to ∼2 eV for oxygen-deficient surfaces. The solvation model predictions are in excellent agreement (within ∼0.1 eV) with ab initio molecular dynamics results where available, and in good agreement (within ∼0.2-0.3 eV) with experimental measurements. We also predict the energetics for surface oxygen vacancies and their effect on the band positions of the hydrated WO3(001) surface, leading to an explanation for why the solvation shift observed experimentally is substantially larger than predicted for the ideal surface. Based on the correlation between solvation shift and the type of surface and solvent, we suggest approaches to engineer the band positions of surfaces in aqueous and non-aqueous solutions.

show abstract

“…Indeed, although the structural [8][9][10] , electronic 7,[11][12][13][14] , conductivity 15,16 and optic [16][17][18][19] properties are well known for the bulk of iridium oxide, there is an evident lack of knowledge regarding the surface properties and the surface reactivity of this material. In particular, an atomic description of the surfaces is missing, limiting the knowledge and the interpretation of the physico-chemical phenomena taking place.…”

Section: Introductionmentioning

confidence: 99%

Periodic DFT Study of Rutile IrO₂: Surface Reactivity and Catechol Adsorption

Matz

Calatayud

2017

J. Phys. Chem. C

View full text Add to dashboard Cite

IrO 2 is a key material for photocatalytic applications as water oxidation catalyst. Despite its increasing interest, little is known about its molecular structure and reactivity. In this study, the surface properties of stoichiometric rutile IrO 2 are investigated by means of periodic density functional theory (DFT), including the structural, energetic, electronic properties and chemical reactivity towards catechol, a probe molecule mimicking photocatalytic linkers. Our results show that the (110)-IrO 2 rutile termination is the most stable, and we discuss the role of the number and type of surface sites in the relative stability compared with (100), (001) and (101) terminations. Regarding the reactivity of the surfaces with catechol, our results show that the molecule dissociates and binds in bidentate, chelate and monodentate modes.Interestingly, we find the chelated mode selectively favored over the (001)

show abstract

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

Cited by 104 publications

References 42 publications

Strong spin-orbit coupling and Dirac nodal lines in the three-dimensional electronic structure of metallic rutile IrO2

Strong spin-orbit coupling and Dirac nodal lines in the three-dimensional electronic structure of metallic rutile IrO2

Solvation effects on the band edge positions of photocatalysts from first principles

Periodic DFT Study of Rutile IrO₂: Surface Reactivity and Catechol Adsorption

Contact Info

Product

Resources

About

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

Cited by 104 publications

References 42 publications

Strong spin-orbit coupling and Dirac nodal lines in the three-dimensional electronic structure of metallic rutile IrO2

Strong spin-orbit coupling and Dirac nodal lines in the three-dimensional electronic structure of metallic rutile IrO2

Solvation effects on the band edge positions of photocatalysts from first principles

Periodic DFT Study of Rutile IrO2: Surface Reactivity and Catechol Adsorption

Contact Info

Product

Resources

About

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

Periodic DFT Study of Rutile IrO₂: Surface Reactivity and Catechol Adsorption