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At least 19 records

Spin-orbit-controlled metal–insulator transition in Sr 2 IrO 4

In the context of correlated insulators, where electron–electron interactions (U) drive the localization of charge carriers, the metal–insulator transition is described as either bandwidth- or filling-controlled. Motivated by the challenge of the insulating phase in Sr 2 IrO 4 , a new class of correlated insulators has been proposed, in which spin–orbit coupling (SOC) is believed to renormalize the bandwidth of the half-filled j eff = 1/2 doublet, allowing a modest U to induce a charge-localized phase. Although this framework has been tacitly assumed, a thorough characterization of the ground state has been elusive. Furthermore, direct evidence for the role of SOC in stabilizing the insulating state has not been established, because previous attempts at revealing the role of SOC have been hindered by concurrently occurring changes to the filling. Here, we overcome this challenge by employing multiple substituents that introduce well-defined changes to the signatures of SOC and carrier concentration in the electronic structure, as well as a new methodology that allows us to monitor SOC directly. Specifically, we study Sr 2 Ir 1-x T x O 4 (T = Ru, Rh) by angle-resolved photoemission spectroscopy, combined with ab initio and supercell tight-binding calculations. This allows us to distinguish relativistic and filling effects, thereby establishing conclusively the central role of SOC in stabilizing the insulating state of Sr 2 IrO 4 . Most importantly, we estimate the critical value for SOC in this system to be λ c = 0.42 ± 0.01 eV, and provide the first demonstration of a spin–orbit-controlled metal–insulator transition.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Theoretical Prediction and Experimental Verification of IrO x Supported on Titanium Nitride for Acidic Oxygen Evolution Reaction

Reducing iridium (Ir) catalyst loading for acidic oxygen evolution reaction (OER) is a critical strategy for large-scale hydrogen production via proton exchange membrane (PEM) water electrolysis. However, simultaneously achieving high activity, long-term stability, and reduced material cost remains challenging. To address this challenge, we develop a frame-work by combining density functional theory (DFT) prediction using model surfaces and proof-of-concept experimental ver-ification using thin films and nanoparticles. DFT results predict that oxidized Ir monolayers over titanium nitride (IrO x /TiN) should display higher OER activity than IrO x while reducing Ir loading. Further, this prediction is verified by depositing Ir monolayers over TiN thin films via physical vapor deposition. The promising thin film results are then extended to commercially viable powder IrO x /TiN catalysts, which demonstrate a lower overpotential and higher mass activity than commercial IrO 2 , and a long-term stability of 250 hours to maintain a current density of 10 mA cm -2 . The superior OER performance of IrO x /TiN is further confirmed using proton exchange membrane water electrolyzer (PEMWE), which shows a lower cell voltage than commercial IrO 2 to achieve a current density of 1 A cm -2 . Both DFT and in situ X-ray absorption spectroscopy reveal that the high OER performance of IrO x /TiN strongly depends on the IrO x - TiN interaction via direct Ir-Ti bonding. This study highlights the importance of close interaction between theoretical prediction based on mechanistic understanding and experimental verification based on thin film model catalysts to facilitate the development of more practical powder IrO x /TiN catalysts with high activity and stability for acidic OER.

08 HYDROGEN↗

Resolution of zigzag magnetic correlations in Na-deficient Na x IrO 3 without long-range ordering

The materials search for Kitaev quantum spin liquids led to the discovery of many honeycomb lattice materials. Much attention has been paid to materials without magnetic order down to the lowest temperatures. The newly synthesized Na-deficient Na x IrO 3 has been found to bear no sign of long-range magnetic order above 1 K from physical property measurements. In this paper, we report momentum-and energy-resolved excitation spectra in Na-deficient Na x IrO 3 measured using a resonant inelastic x-ray scattering spectrometer. Orbital excitation spectra show that the octahedral and trigonal crystal field splittings are larger in Na x IrO 3 than in Na 2 IrO 3 . On the other hand, the low-energy spectrum at low temperature shows a wave-vector dispersion and a spectral weight distribution that are similar to those of Na 2 IrO 3 , revealing that the two-dimensional zigzag magnetic correlations in Na x IrO 3 are similar to those in Na 2 IrO 3 in terms of the ordered magnetic moment direction and three dynamically fluctuating zigzag orders. The azimuth angle dependence of the low-energy spectrum corroborates these results. The two-dimensional zigzag magnetic correlations rapidly weaken until 50 K. At high temperatures, the spectral weight distribution of the low-energy excitation resembles that of the pure Kitaev model, indicating that the Kitaev interaction dominates the dynamic magnetic response at high temperature. Here we suggest that the larger crystal field and distortion and the weakened longer-range Heisenberg exchange interactions due to the Na deficiency in Na x IrO 3 contribute to bring Na x IrO 3 away from the zigzag long-range magnetic order phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evolution of Oxygen Ligands upon Large Redox Swings of Li 3 IrO 4

The limits of intercalation electrochemistry continue to be tested in the quest for ever increasing gains in the storage capability of Li-ion cathodes. The subsequent push for multi-electron reactivity has led to the recognition of the extremely versatile role of oxide ligands in charge compensation when there is a large redox swing. Li 3 IrO 4 is a unique model of such activity because it can reversibly cycle between Li 1 IrO 4 and Li 4.7 IrO 4 . In this study, X-ray spectroscopy, magnetic measurements and computational simulations uncover the evolution of O states in the different steps, compared to the involvement of Ir. While the process between Li 1 IrO 4 and Li 3 IrO 4 is dominated by the unconventional lattice oxygen redox, the process between Li 3 IrO 4 and Li 4.7 IrO 4 involves a conventional change of the formal oxidation state of Ir, which affects O due to the high covalency. The O states of Li 3 IrO 4 exhibit a very high reversibility after the whole 3.7-electron process, completely restoring the pristine state.

25 ENERGY STORAGE↗

Non-Centrosymmetric Sr 2 IrO 4 Obtained Under High Pressure

Sr 2 IrO 4 with strong spin-orbit coupling (SOC) and Hubbard repulsion (U) hosts Mott insulating states. The similar crystal structure, magnetic and electronic properties, particularly the d-wave gap observed in Sr 2 IrO 4 enhanced the analogies to cuprate high-$T_c$ superconductor, La 2 CuO 4 . The incomplete analogy was due to the lack of broken inversion symmetry phases observed in Sr 2 IrO 4 . Here, under high pressure and high temperature conditions, we report a non-centrosymmetric Sr 2 IrO 4 . The crystal structure and its noncentrosymmetric character were determined by single crystal X-ray diffraction and high-resolution scanning transmission electron microscopy (HR-STEM). The magnetic characterization confirms the Ir 4+ with $\textit{S}$ = 1/2 at low temperature in Sr 2 IrO 4 with magnetic ordering occurred at around 86 K, where a larger moment is observed than the ambient pressure Sr 2 IrO 4 . Moreover, the resistivity measurement shows three-dimensional Mott variable-range hopping existed in the system. Further, this non-centrosymmetric Sr 2 IrO 4 phase appears to be a unique material to offer further understanding of high-$T_c$ superconductivity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Magnetic excitations in the square-lattice iridate Ba 2 ⁢IrO 4

Here, we report a resonant inelastic x-ray scattering investigation of ultrathin epitaxial films of Ba 2 ⁢IrO 4 , and compare their low-energy magnetic and spin-orbit excitations to those of their sister compound Sr 2 ⁢IrO 4 . Due to the 180° Ir-O-Ir bond, the bandwidth of the magnon and spin orbiton is significantly larger in Ba 2⁢ IrO 4 , making it difficult to describe these two types of excitations as separate well-defined quasiparticles. Both types of excitations are found to be quite sensitive to the effect of epitaxial strain. In addition, we find that the f-level inversion observed in Sr 2 ⁢IrO 4 is absent in Ba 2 ⁢IrO 4 , as predicted in recent theoretical studies. Our results illustrate that the magnetic properties of Ba 2 ⁢IrO 4 are substantially different from those of Sr 2 ⁢IrO 4 , suggesting that these materials need to be examined more carefully with electron itinerancy taken into account.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Emergent Epitaxial Configuration of Pr 3 IrO 7 Domains via YSZ (111) Substrate

The 5d rare Earth iridate is an intriguing material with exhibiting exotic electronic and magnetic phases due to spin-orbit coupled states. Ternary iridium oxides Ln 3 IrO 7 contain an unusual Ir 5+ (5d 4 ) system, which remain a subject of active research. Fabricating epitaxial Ln 3 IrO 7 films is challenging due to substrate compatibility, but it offers a valuable platform to explore electronic and magnetic behaviors under reduced dimensionality and substrate interactions, revealing novel phenomena based on Ir 5+ (5d 4 ). In this regard, this demonstrates that Pr 3 IrO 7 with its highly anisotropic orthorhombic structure can be epitaxially grown on a cubic (111)-oriented yttrium-stabilized ZrO 2 (YSZ) substrate. Pr 3 IrO 7 film exhibits six epitaxial domains, where the (220) and (202) planes aligning epitaxially to YSZ (111) with the threefold symmetry. This diverse domain configuration in Pr 3 IrO 7 film leads to unique magnetic properties, exhibiting spin-glass-like behavior. Pr 3 IrO 7 thin film offers a platform for exploring unconventional magnetic states, and their successful heteroepitaxy on YSZ substrates opens new avenues for discovering novel physical phenomena.

36 MATERIALS SCIENCE↗

Composition, Activity, and Stability of IrO x Oxygen Evolution Reaction Electrocatalysts

The oxygen evolution reaction (OER) is integral to several electrochemical energy conversion and storage technologies, including carbon dioxide reduction to value added fuels, nitrogen reduction to ammonia, reversible fuel cells, rechargeable metal−air batteries, and water electrolysis to produce hydrogen. Iridium oxide (IrO x ) is widely recognized as the benchmark OER catalyst for acidic environments. Despite widespread use of IrO x catalysts, most notably in proton-exchange membrane water electrolyzers (PEMWEs), a comprehensive understanding of the physicochemical properties of commercial catalysts and the impact of these properties on both the activity and stability of these catalysts is lacking. Here, we study commercial IrO x catalysts with different physicochemical properties, three nominally considered amorphous and three rutile, to elucidate how structural and compositional variations affect OER activity and stability. Utilizing standardized aqueous electrochemical protocols, time-resolved dissolution quantification using inductively-coupled plasma mass spectrometry, and physicochemical characterization, including multiple synchrotron X-ray techniques, we systematically correlate catalyst properties with OER performance and degradation behavior aided by principal component analysis (PCA). Our results demonstrate the general trend of amorphous IrO x having higher intrinsic activity but limited stability and crystalline rutile IrO 2 having lower activity but enhanced stability against dissolution. The trends within the amorphous and rutile catalyst groups correlate with inherent material properties, including phase composition and structure, crystallinity, particle size, surface area, and surface structure/chemistry. Notably, we identify a rutile catalyst with the largest crystallite/ domain sizes, moderate surface area, a small fraction of hydrous phase, and a favorable pore structure (trimodal distributions of pore sizes ranging from 2−5 nm) that exhibits the best balance between activity and stability among the six catalysts studied here. These findings illustrate a fundamental structure-governed trade-off between activity and stability and highlight the critical role of surface chemistry modification and structure engineering in IrO x catalyst optimization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design-controlled synthesis of IrO 2 sub-monolayers on Au nanoflowers: marrying plasmonic and electrocatalytic properties

We develop herein plasmonic–catalytic Au–IrO 2 nanostructures with a morphology optimized for efficient light harvesting and catalytic surface area; the nanoparticles have a nanoflower morphology, with closely spaced Au branches all partially covered by an ultrathin (1 nm) IrO 2 shell. This nanoparticle architecture optimizes optical features due to the interactions of closely spaced plasmonic branches forming electromagnetic hot spots, and the ultra-thin IrO 2 layer maximizes efficient use of this expensive catalyst. This concept was evaluated towards the enhancement of the electrocatalytic performances towards the oxygen evolution reaction (OER) as a model transformation. The OER can play a central role in meeting future energy demands but the performance of conventional electrocatalysts in this reaction is limited by the sluggish OER kinetics. We demonstrate an improvement of the OER performance for one of the most active OER catalysts, IrO 2 , by harvesting plasmonic effects from visible light illumination in multimetallic nanoparticles. We find that the OER activity for the Au–IrO 2 nanoflowers can be improved under LSPR excitation, matching best properties reported in the literature. Our simulations and electrocatalytic data demonstrate that the enhancement in OER activities can be attributed to an electronic interaction between Au and IrO 2 and to the activation of Ir–O bonds by LSPR excited hot holes, leading to a change in the reaction mechanism (rate-determinant step) under visible light illumination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular chemisorption of N 2 on IrO 2 (110)

We investigated the adsorption of N 2 on stoichiometric and O-rich IrO 2 (110) surfaces using temperature programmed desorption (TPD) experiments and density functional theory (DFT) calculations. TPD shows that N 2 desorbs predominantly from the stoichiometric-IrO 2 (110) surface in a well-defined peak at 270 K for N 2 coverages below about 0.5 ML, and that a shoulder centered near 235 K develops in the N 2 TPD traces as the coverage approaches saturation, indicating that adsorbed N 2 molecules become destabilized at high N 2 coverage. Experiments of N 2 adsorption onto O-rich IrO 2 (110) surfaces provide evidence that N 2 adsorbs exclusively on the coordinatively-unsaturated Ir atoms (Ircus) of the surface, and that pre-adsorbed O-atoms (“on-top” oxygen) stabilize adsorbed N 2 molecules, causing the main N 2 TPD peak to shift toward higher temperature with increasing oxygen coverage. Consistent with prior results, our DFT calculations predict that an N 2 molecule preferentially adsorbs into an upright configuration on an Ircus atom of the IrO 2 (110) surface and achieves a binding energy of about 100 kJ/mol. The computed binding energy agrees well with our experimental estimate of ~90 kJ/mol for low N 2 coverages on stoichiometric IrO 2 (110). Lastly, the DFT calculations also quantitatively reproduce the observed stabilization of N 2 by co-adsorbed on-top O-atoms and predict the destabilization of N 2 on IrO 2 (110) as the N 2 adlayer becomes crowded at high coverage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ground state in proximity to a possible Kitaev spin liquid: The undistorted honeycomb iridate Na x IrO 3 (0.60 ≤ x ≤ 0.80)

Here, we report the results of our study of a recently synthesized honeycomb iridate Na x IrO 3 (0.60 ≤ x ≤ 0.80). Single-crystal Na x IrO 3 adopts a honeycomb lattice noticeably without distortions and stacking disorder inherently existent in its sister compound Na 2 IrO 3 . The oxidation state of the Ir ion is a mixed valence state resulting from a majority Ir 5+ (5d 4 ) ion and a minority Ir 6+ (5d 3 ) ion. Na x IrO 3 is a Mott insulator likely with a predominant pseudospin =1 state. It exhibits an effective moment of 1.1 μB/Ir and a Curie-Weiss temperature of –19 K but with no discernible long-range order above 1 K. The physical behavior below 1 K features two prominent anomalies at T h = 0.9 K and T l = 0.12 K in both the heat capacity and AC magnetic susceptibility. Intermediate between T h and T l lies a pronounced temperature linearity of the heat capacity with a large slope of 77 mJ /mole K 2 , a feature expected for highly correlated metals but not at all for insulators. These results along with a comparison drawn with the honeycomb lattices Na 2 IrO 3 and (Na 0.2 Li 0.8 ) 2 IrO 3 point to an exotic ground state in proximity to a possible Kitaev spin liquid.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Rationalizing Acidic Oxygen Evolution Reaction over IrO 2 : Essential Role of Hydronium Cation

Abstract The development of active, stable, and more affordable electrocatalysts for acidic oxygen evolution reaction (OER) is of great importance for the practical application of electrolyzers and the advancement of renewable energy conversion technologies. Currently, IrO 2 is the only catalyst with high stability and activity, but a high cost. Further optimization of the catalyst is limited by the lack of understanding of catalytic behaviors at the acid‐IrO 2 interface. Here, in strong interaction with the experiment, we develop an explicit model based on grand‐canonical density function theory (GC‐DFT) calculations to describe acidic OER over IrO 2 . Compared to the explicit models reported previously, hydronium cations (H 3 O + ) are introduced at the electrochemical interface in the current model. As a result, a variation in stable IrO 2 surface configuration under the OER operating condition from previously proposed complete *O‐coverage to a mixture coverage of *OH and *O is revealed, which is well supported by in situ Raman measurements. In addition, the accuracy of predicted overpotential is increased in comparison with the experimentally measured. More importantly, an alteration of the potential limiting step from previously identified *O→*OOH to *OH→*O is observed, which opens new opportunities to advance the IrO 2 ‐based catalysts for acidic OER.

Mou, Tianyou↗

Rationalizing Acidic Oxygen Evolution Reaction over IrO 2 : Essential Role of Hydronium Cation

The development of active, stable, and more affordable electrocatalysts for acidic oxygen evolution reaction (OER) is of great importance for the practical application of electrolyzers and the advancement of renewable energy conversion technologies. Currently, IrO 2 is the only catalyst with high stability and activity, but a high cost. Further optimization of the catalyst is limited by the lack of understanding of catalytic behaviors at the acid-IrO 2 interface. Here, in strong interaction with the experiment, we develop an explicit model based on grand-canonical density function theory (GC-DFT) calculations to describe acidic OER over IrO 2 . Compared to the explicit models reported previously, hydronium cations (H 3 O + ) are introduced at the electrochemical interface in the current model. As a result, a variation in stable IrO 2 surface configuration under the OER operating condition from previously proposed complete *O-coverage to a mixture coverage of *OH and *O is revealed, which is well supported by in situ Raman measurements. In addition, the accuracy of predicted overpotential is increased in comparison with the experimentally measured. More importantly, in this study, an alteration of the potential limiting step from previously identified *O→*OOH to *OH→*O is observed, which opens new opportunities to advance the IrO 2 -based catalysts for acidic OER.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Kinetics of low-temperature methane activation on IrO 2 (1 1 0): Role of local surface hydroxide species

The ability of the IrO 2 (1 1 0) surface to promote CH 4 activation at low temperatures (~150 K) suggests possibilities for developing IrO 2 -based catalysts to selectively convert light alkanes to high-value chemicals. In this study, we present experimental results and microkinetic simulations, based on density functional theory (DFT) calculations, of temperature programmed reaction spectra (TPRS) obtained for CH 4 σ-complexes adsorbed on IrO 2 (1 1 0), and focus on clarifying how surface OH groups modify the branching between CH 4 desorption, activation and subsequent reactions during TPRS. Our DFT results predict that surface OH groups strongly destabilize CH 4 σ-complexes on IrO 2 (1 1 0) in addition to deactivating surface O-atoms that are needed to achieve CH 4 activation at low temperature. We demonstrate that a microkinetic model that incorporates the influence of surface OH groups on the CH 4 binding and reactivity reproduces experimental TPRS results which show that adsorbed CH 4 σ-complexes preferentially dissociate at low CH 4 coverage, but that an increasing fraction of the adsorbed CH 4 desorbs at low temperature (~120 K) with increasing initial CH 4 or H coverage. The simulations reveal that low-temperature CH4 desorption during TPRS arises primarily from CH 4 σ-complexes that are kinetically-trapped between adjacent surface OH groups, and are thus destabilized and unable to access reactive O-atoms. In addition, when the effect of adjacent OH groups is incorporated we find that the PBE-D3 functional incorporating dispersion provides CH 4 binding energies that agree more closely with that obtained from the TPRS experiments. Overall, our results demonstrate that the local effect of adjacent OH groups must be incorporated into any microkinetic models to properly capture the selectivity between extensive and partial oxidation in alkane conversion on IrO 2 (1 1 0) under reaction conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhanced Selectivity for C 2 H 4 Production from C 2 H 6 on Partially Chlorinated IrO 2 (110) Surfaces

Modifying metal oxide surfaces to limit their oxidizing activity can provide a means of improving catalytic selectivity toward the partial oxidation of light alkanes. Here, in this study, we investigated the oxidation of C 2 H 6 on Cl-modified IrO 2 (110) surfaces using temperature-programmed reaction spectroscopy (TPRS) and first-principles microkinetic modeling. We find that substituting Cl for O in the IrO 2 (110) surface enhances the selectivity for C 2 H 6 conversion to C 2 H 4 during TPRS by suppressing extensive oxidation to CO x products, while also either enhancing C 2 H 4 production or altering it to a lesser extent, depending on the initial C 2 H 6 coverage. The C 2 H 4 selectivity increased with increasing C 2 H 6 and Cl coverage, but reached a limiting value below 50%. The Cl coverage changed negligibly during C 2 H 6 oxidation, and the surface reactivity decreased only marginally for Cl coverages up to 0.5 ML (monolayer). TPRS simulations using a microkinetic model predict C 2 H 4 and CO x product yields as a function of the Cl coverage that agree closely with the experimental results. According to the simulations, C 2 H 6 conversion to C 2 H 4 occurs on Cl-IrO 2 (110) by the hydrogenation of C 2 H 3 * species adsorbed in blocked states, in which neighboring sites are occupied only by unreactive HO and Cl species. The microkinetic modeling shows that H-hopping away from surface HO groups provides a relatively efficient route for C 2 H 3 * to escape blocked configurations and dehydrogenate, and that this process can limit the C 2 H 4 selectivity on Cl-IrO 2 (110) under the conditions studied. Overall, our results demonstrate that Cl-substitution into IrO 2 (110) enhances the selectivity for C 2 H 4 production from C 2 H 6 and provides insights into the reaction mechanism that can guide strategies to further improve the C 2 H 4 selectivity.

IrO2↗

Kinetics and selectivity of methane oxidation on an IrO 2 (110) film

Undercoordinated, bridging O-atoms (O br ) are highly active as H-acceptors in alkane dehydrogenation on IrO 2 (110) surfaces but transform to HO br groups that are inactive toward hydrocarbons. The low C–H activity and high stability of the HO br groups cause the kinetics and product selectivity during CH 4 oxidation on IrO 2 (110) to depend sensitively on the availability of O br atoms prior to the onset of product desorption. From temperature programmed reaction spectroscopy (TPRS) and kinetic simulations, we identified two O br -coverage regimes that distinguish the kinetics and product formation during CH 4 oxidation on IrO 2 (110). Under excess O br conditions, when the initial O br coverage is greater than that needed to oxidize all the CH 4 to CO 2 and HO br groups, complete CH 4 oxidation is dominant and produces CO 2 in a single TPRS peak between 450 and 500 K. However, under O br -limited conditions, nearly all the initial O br atoms are deactivated by conversion to HO br or abstracted after only a fraction of the initially adsorbed CH 4 oxidizes to CO 2 and CO below 500 K. Thereafter, some of the excess CH x groups abstract H and desorb as CH 4 above ~500 K while the remainder oxidize to CO 2 and CO at a rate that is controlled by the rate at which Obr atoms are regenerated from HObr during the formation of CH 4 and H 2 O products. We also show that chemisorbed O-atoms ('on-top O') on IrO 2 (110) enhance CO 2 production below 500 K by efficiently abstracting H from Obr atoms and thereby increasing the coverage of O br atoms available to completely oxidize CH x groups at low temperature. Furthermore, our results provide new insights for understanding factors which govern the kinetics and selectivity during CH 4 oxidation on IrO 2 (110) surfaces.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Competition between magnetic order and charge localization in Na 2 IrO 3 thin crystal devices thin crystal devices

Spin orbit assisted Mott insulators such as sodium iridate (Na 2 IrO 3 ) have been an important subject of study in recent years. In these materials, the interplay of electronic correlations, spin-orbit coupling, crystal field effects, and a honeycomb arrangement of ions bring exciting ground states, predicted in the frame of the Kitaev model. The insulating character of Na 2 IrO 3 has hampered its integration to an electronic device, desirable for applications, such as the manipulation of quasiparticles interesting for topological quantum computing. Here we show through electronic transport measurements supported by angle-resolved photoemission spectroscopy (ARPES) experiments, that electronic transport in Na 2 IrO 3 is ruled by variable range hopping and it is strongly dependent on the magnetic ordering transition known for bulk Na 2 IrO 3 , as well as on external electric fields. Furthermore, electronic transport measurements allow us to deduce a value for the localization length and the density of states in our Na 2 IrO 3 thin crystal devices, and offer an alternative approach to study insulating 2D-materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Unveiling the Role of Surface Ir-Oxo Species in O 2 Evolution at IrO 2 Electrocatalysts via Embedded Cluster Multireference Calculations

Understanding the mechanisms driving the oxygen evolution reaction (OER) on iridium oxide (IrO 2 )-based catalysts is essential to improving their performance and enabling an actual scale-up of water-splitting photoelectrochemical cells. The mechanistic pathways at IrO 2 interfaces have been extensively investigated computationally using density functional theory (DFT), which predicts a high-energy barrier for the last step of the OER of molecular oxygen detachment and release from the catalyst surface. Nevertheless, surface O 2 over- and under-binding results by standard generalized gradient approximation and hybrid density functionals, respectively, call for further analysis of this crucial step via multireference methods. Aiming at unveiling the nature of such a barrier, we hereby address the formation of O 2 from the most-stable IrO 2 (110) surface with both periodic DFT and an electrostatic embedded cluster approach at the n-electron valence-state perturbation theory. With this multireference approach, we find a value for the aforementioned energy barrier that is much closer to experimental indications than DFT ones. Here, an in-depth analysis of the involved molecular orbitals suggests that the origin of this barrier is related to the breaking of a π interaction between O 2 and Ir surface atom and to a significant additional O 2 interaction with adjacent electrophilic Ir-oxo species, which is present under experimental operating conditions. Besides shedding light on the mechanism of the OER on IrO 2 , these findings point out the importance of multireference methods for dissecting complex reactions at electrocatalytic interfaces and pave the route for further investigations with effective embedding approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗