High-Resolution X-ray Photoelectron Spectroscopy of an IrO2(110) Film on Ir(100)
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99 GENERAL AND MISCELLANEOUS↗
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Microwave-Assisted Synthesis of Cu@IrO 2 Core-Shell Nanowires for Low-Temperature Methane Conversion
A facile microwave-assisted synthesis was developed for the tunable fabrication of a novel Cu@IrO 2 core@shell nanowire motif. Experimental parameters, such as (i) reaction time, (ii) the method of addition of the Ir precursor, (iii) capping agent, (iv) reducing agent, as well as (v) the capping agent-to-reducing agent ratio, were subsequently optimized. The viability of other methods based on previously reported literature, such as refluxing, stirring, and physical sonication, was studied and compared with our optimized microwave-assisted protocol in creating our as-prepared materials. It should be noted that the magnitude of the IrO 2 shell could be tailored based on varying the Cu: Ir ratio coupled with judicious variations in the amounts of capping agent and reducing agent. Structural characterization techniques, such as XRD, XPS, and HRTEM (including HRTEM-EDS), were used to analyze our Cu@IrO 2 motifs. Specifically, the shell could be reliably tailored from sizes of 10 nm, 8 nm, 6 nm, and 3.5 nm with corresponding Cu: Ir ratios of 10:1, 15:1, 20:1, and 25:1, respectively. Moreover, the structural integrity of the motifs was probed and found to have been maintained after not only heat treatment but also the post-methane conversion process, indicative of an intrinsically high stability. Both components within the CuO-IrO 2 interface were able to activate methane at temperatures between 400 to 500 K with a reduction of the associated metal cations (Cu 2+ → Cu 1+ ; Ir 4+ → Ir 3+ ) and the deposition of CH x fragments on the surface, as clearly observed in the ambient-pressure XPS results. Thus, on the basis of their stability and chemical activity, these core-shell materials could be very useful for the catalytic conversion of methane into 'higher value" chemicals.
36 MATERIALS SCIENCE↗
Electronic nature of the pseudogap in electron-doped Sr 2 IrO 4
In high-temperature ($T_c$) cuprate superconductors, many exotic phenomena are rooted in the enigmatic pseudogap state, which has been interpreted as consisting of preformed Cooper pairs or competing orders or a combination thereof. Observation of pseudogap phenomenologically in electron-doped Sr 2 IrO 4 —the 5d electron counterpart of the cuprates, has spurred intense interest in the strontium iridates as a testbed for exploring the exotic physics of the cuprates. Here, we examine the pseudogap state of electron-doped Sr 2 IrO 4 by angle-resolved photoemission spectroscopy (ARPES) and parallel theoretical modeling. Our analysis demonstrates that the pseudogap state of Sr 2 IrO 4 appears without breaking the particle–hole symmetry or inducing spectral broadening which are telltale signatures of competing orders in the cuprates. We find quasiparticle dispersion and its temperature dependence in the pseudogap state of Sr 2 IrO 4 to point to an electronic order with a zero scattering wave vector and limited correlation length. Particle–hole symmetric preformed Cooper pairs are discussed as a viable mechanism for such an electronic order. The potential roles of incommensurate density waves are also discussed.
36 MATERIALS SCIENCE↗
Molecular beam epitaxy growth of IrO 2 using plasma-only oxidation
Growth of IrO 2 films via molecular beam epitaxy (MBE) using an oxygen plasma as the sole oxidant is demonstrated for the first time. We investigate the oxidizing conditions required for IrO 2 by characterizing the species present in the plasma using optical emission spectroscopy and comparing the thermodynamic equilibrium between Ir/IrO 2 under atomic and molecular oxygen. Across the pressure range accessible, monatomic oxygen was the primary reactive species present in the plasma. IrO 2 films were grown under varying Ir flux, oxygen pressure, and substrate temperature to understand growth thermodynamics and kinetics. Structural characterization assessed film phase and composition, crystallinity, strain, and surface morphology. The optimized films from this study validate plasma-only reactive growth by MBE as a successful method for growing IrO 2 .
36 MATERIALS SCIENCE↗
The ionomer as an oxygen evolution reaction promoter: piperidinium’s impact on mechanistic pathways on NiO, IrO 2 , and Fe–NiO
The commercial viability of anion exchange membrane (AEM) electrolysis requires optimization of various stack components, with specific catalyst-ionomer combinations often yielding higher current densities, lowered Tafel slopes, and improved mass activity. In this joint theoretical-experimental study, theoretical calculations detail the impact of Versogen’s piperidinium functional group on the complex, kinetically limiting oxygen evolution reaction, finding that the functional group can act as a promoter of specific steps (O*/O 2 * formation; H 2 O/O 2 desorption with reaction enthalpies ranging between 0.2–0.6 eV at higher coverages of O x H y intermediates) on NiO and NiFeO x catalysts. In particular, Fe sites on the NiFeO x catalyst facilitate concerted mechanisms of O*/O 2 * formation and H 2 O desorption with a low enthalpy of 0.5 eV; O 2 desorption alone requires only 0.3 eV. In contrast, Versogen-IrO 2 results in stronger Ir–O bonds, where the enthalpies for bond breaking (Ir–OH 2 and Ir–O 2 ) are considerably higher (1.4 eV and 1.6 eV, respectively). Rotating disk electrode studies utilized commercially available NiO and IrO 2 and synthesized 7.5 wt % Fe in NiFeO x catalysts in combination with Versogen, a common AEM ionomer, and Nafion, an alternative binder. Electrochemical testing validated the impact of these mechanistic changes on ionomer-catalyst combinations, finding that Versogen particularly activates NiO and NiFeO x compared to IrO 2 . Following a 13.5 h hold at 1.8 V, mass activities and Tafel slopes improved to 34 ± 13 A g −1 and 79 ± 2 mV dec −1 (NiO) and 82 ± 4.9 A g −1 and 72 ± 2 mV dec −1 (NiFeO x ). In contrast, Versogen-IrO 2 only reached 17 ± 2.9 A g −1 and 81 ± 3 mV dec −1 . Optimization of the ionomer-catalyst can yield significant increases in performance from initial activity and after an electrochemical conditioning procedure: this enhancement to the mass activity resulted in a 200.9 ± 106.1% improvement for Versogen-NiFeO x and 1284.2 ± 260.5% for Versogen-NiO. In contrast, Nafion-NiFeO x and -NiO offered moderate improvements of 39.1 ± 30.5% and 120.9 ± 59.1%, respectively.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Emergent interlayer magnetic order via strain-induced orthorhombic distortion in the 5 d Mott insulator Sr 2 IrO 4
In this letter, we report a La 2 CuO 4 -like interlayer antiferromagnetic order in Sr2IrO4 films with large orthorhombic distortion (>1.5%). The biaxial lattice strain in epitaxial heterostructures of Sr 2 IrO 4 /Ca 3 Ru 2 O 7 lowers the crystal symmetry of Sr 2 IrO 4 from tetragonal ($C_4$) to orthorhombic ($C_2$), guiding the Ir $5d J_{text{eff}}$ = 1/2 pseudospin moment parallel to the elongated b axis via magnetic anisotropy. From resonant x-ray scattering experiments, we observed an antiferromagnetic order in the orthorhombic Sr 2 IrO 4 film whose interlayer stacking pattern is inverted from that of the tetragonal Sr 2 IrO 4 crystal. This interlayer stacking is similar to that of the orthorhombic La 2 CuO 4 , implying that the asymmetric interlayer exchange interactions between $\textit{a}$ and $\textit{b}$ directions exceed the anisotropic interlayer pseudodipolar interaction. Our result suggests that strain-induced distortion can provide a delicate knob for tuning the long-range magnetic order in quasi-two-dimensional systems by evoking the competition between the interlayer exchange coupling and the pseudodipolar interaction.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Possible Quantum Paramagnetism in Compressed Sr 2 IrO 4
The result of compression on the magnetic ground state of Sr 2 IrO 4 is studied with x-ray resonant techniques in the diamond anvil cell. The weak interlayer exchange coupling between square-planar 2D IrO 2 layers is easily modified upon compression, with a crossover between magnetic structures around 7 GPa mimicking the effect of an applied magnetic field at ambient pressure. Higher pressures drive an order-disorder magnetic phase transition with no magnetic order detected above 17–20 GPa. The persistence of strong exchange interactions between J eff = 1 / 2 magnetic moments within the insulating IrO 2 layers up to at least 35 GPa points to a highly frustrated magnetic state in compressed Sr 2 IrO 4 , opening the door for realization of novel quantum paramagnetic phases driven by extended 5 d orbitals with entangled spin and orbital degrees of freedom.
36 MATERIALS SCIENCE↗
On the Role of Interfacial Water Dynamics for Electrochemical Stability of RuO 2 and IrO 2
Abstract Based on the coincident onsets of oxygen evolution reaction (OER) and metal dissolution for many metal‐oxide catalysts it was suggested that OER triggers dissolution. It is believed that both processes share common intermediates, yet exact mechanistic details remain largely unknown. For example, there is still no clear understanding as to why rutile IrO 2 exhibits such an exquisite stability among water‐splitting electrocatalysts. Here, we employ density functional theory calculations to analyze interactions between water and the (110) surface of rutile RuO 2 and IrO 2 as a response to oxygen evolution involving lattice oxygen species. We observe that these oxides display qualitatively different interfacial behavior that should have important implications for their electrochemical stability. Specifically, it is found that IrO 2 (110) becomes further stabilized under OER conditions due to the tendency to form highly stable low oxidation state Ir(III) species. In contrast, Ru species at RuO 2 (110) are prone to facile reoxidation by solution water. This should facilitate the formation of high Ru oxidation state intermediates (>IV) accelerating surface restructuring and metal dissolution.
Evazzade, Iman↗
Evaluation of IrO 2 catalysts doped with Ti and Nb at industrially relevant electrolyzer conditions: A comprehensive study
A series of commercial Oxygen Evolution Reaction (OER) IrO 2 -based materials doped with acid-stable titanium and niobium species were comprehensively characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction analysis (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS), and X-ray Scattering. Electrocatalysts were integrated into Membrane Electrode Assembly (MEA) using a fabrication method developed under the US DOE H2NEW consortium. An electrolysis performance in a commercial setup as well as a laboratory screening system was performed at conditions relevant to industrial application. According to the comprehensive characterizations, the studied materials are closer to doped iridium oxides rather than core–shell structures. In an electrolysis cell, the IrO 2 /TiO x catalyst slightly outperforms the IrO 2 /NbO x based on the activity. It was demonstrated that the operation of electrolysis cells at elevated temperatures and the implementation of thinner Nafion-type membranes allows for substantially increased performance, which is consistent with the literature report. Finally, this work provides valuable baselines including characterization and performance for guiding future research in this direction.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surface intermediates identified using IR spectroscopy during the catalytic oxidation of C 2 H 6 on IrO 2 (1 1 0) at near-ambient pressures
Characterizing surface intermediates during catalysis is essential for developing mechanistic models of catalytic reactions and for identifying rate-controlling steps. Here, in this work, we used polarization-dependent reflection absorption infrared spectroscopy (PD-RAIRS) to investigate surface intermediates that form on IrO 2 (1 1 0) during the catalytic oxidation of C 2 H 6 at pressures near 0.5 Torr. Our results show that adsorbed CO and HCO 2 are the only intermediates detectable with PD-RAIRS across a wide range of temperatures and reactant compositions during complete C 2 H 6 oxidation, giving rise to dominant peaks at about 2093 and 1310 cm −1 , respectively. These assignments were corroborated by RAIRS measurements following CO and HCOOH adsorption in ultrahigh vacuum, RAIRS with C 2 H 6 – 18 O 2 mixtures during catalysis and vibrational frequencies and IR intensities computed using density functional theory. We find that increasing the C 2 H 6 mole fraction in the reaction mixture raises the CO surface coverage relative to HCO 2 , correlating with increasing catalytic oxidation rates. The formation of CO and HCO 2 surface species at temperatures well below catalytic ignition indicates that the overall rate of C 2 H 6 oxidation on IrO 2 (1 1 0) is governed by steps late in the reaction sequence, such as H 2 O formation, CO oxidation and HCO 2 dehydrogenation. These findings provide key insight into the mechanism of alkane oxidation on IrO 2 (1 1 0) and valuable input for first-principles microkinetic modeling.
Pope, Connor [Univ. of Florida, Gainesville, FL (U↗
Nanometer-Thick Sr 2 IrO 4 Freestanding Films for Flexible Electronics
In this article, we report the structural and optical properties of nanoscale Sr 2 IrO 4 freestanding thin-films fabricated using a water-soluble Sr 3 Al 2 O 6 layer. The coherent lattice structure, phonon modes, two-magnon Raman scattering, and optical absorption spectra of the Sr 2 IrO 4 nanomembrane are analogous to those of the layered iridate epitaxial thin-films and single crystals. Remarkably, the formation of 3-unit-cell-thick SrIrO 3 and interfacial composite layers alleviates the antiphase boundaries at the Sr 2 IrO 4 /Sr 3 Al 2 O 6 interface, resulting in structurally-robust nanomembranes. Our experimental results show that this freestanding thin-film approach of layered oxides can provide techniques for tuning or realizing unprecedented states beyond conventional thin-film methods, suggesting a pathway in achieving flexible layered-oxide electronics.
36 MATERIALS SCIENCE↗
Confinement Reconstruction Unlocks Stable Ru Single Atom-Doped IrO x Anodes for Long-Term High-Rate CO 2 Electrolysis
IrO 2 is a commonly employed anode catalyst for CO 2 electrolysis in membrane electrode assembly (MEA) systems. However, under high current densities, its structural reconstruction leads to activity loss and stability degradation, limiting the industrial viability of CO 2 electrolysis. In this work, we demonstrated a confinement reconstruction strategy to precisely regulate the structural evolution during electrolysis. Ethylene glycol serves as a structural modulator, protecting the catalyst surface, suppressing soluble species formation, and promoting ordered structural evolution. Single-atom Ru acts as a stability enhancer, forming robust Ir–O–Ru bridging structures that facilitate an ordered transformation from a 4-fold [RuO 4 ]/[IrO 4 ] to a 6-fold symmetry [RuO 6 ]/[IrO 6 ] octahedral framework, thereby enhancing structural rigidity and long-term stability. As a result, in MEA-based CO 2 electrolysis, the catalyst achieves a stable operation at 200 mA cm –2 for 480 h, maintaining a CO selectivity above 80%. Theoretical calculations further elucidate that the enhanced stability originates from the suppression of oxygen vacancy formation, making the lattice-oxygen-mediated mechanism (LOM) potentially less favorable. This work provides insights into the structural evolution of the OER catalysts under high-current-density conditions, paving the way for large-scale CO 2 electrolysis commercialization.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Coexistence of unconventional spin Hall effect and antisymmetric planar Hall effect in IrO 2
Crystal symmetry plays an important role in the Hall effects. Unconventional spin Hall effect (USHE), characterized by Dresselhaus and out-of-plane spins, has been observed in materials with low crystal symmetry. Recently, antisymmetric planar Hall effect (APHE) was discovered in rutile RuO 2 and IrO 2 (101) thin films, which also exhibit low crystal symmetry. In this study, we report the observation of both USHE and APHE in IrO 2 (111) films, using spin-torque ferromagnetic resonance and harmonic Hall measurements, respectively. Notably, the unconventional spin-torque efficiency from Dresselhaus spin was more than double that of a previous report. Additionally, the temperature dependence of APHE suggests that it arises from the Lorentz force, constrained by crystal symmetry. Here, symmetry analysis supports the coexistence of USHE and APHE and demonstrates that both originate from the crystal symmetry of IrO 2 (111), paving the way for a deeper understanding of Hall effects and related physical phenomena.
Crystal structure↗
Facet-dependent structure and dissociation of water at pristine IrO 2 /water interfaces
Understanding the microscopic structure of water at metal oxide interfaces is crucial for advancing electrocatalysis. IrO 2 , specifically, has shown exceptional activity for electrochemical water oxidation, but we currently lack a fundamental understanding of how the surface structure of IrO 2 impacts water reactivity. In this work, we developed a machine learning potential trained to first-principles accuracy for modeling IrO 2 /water interfaces across different facets: (110), (100), (101), and (001). Using extensive machine learning molecular dynamics simulations, we investigated the spontaneous dissociation of water molecules at these interfaces. Our results reveal a distinct dissociation probability trend: (110) > (100) ≈ (101) > (001), which we attribute primarily to the reaction thermodynamics of surface water dissociation. A strong correlation is observed between the surface Ir–O bond distances and the dissociation probabilities, highlighting the role of surface geometry in modulating reactivity. As a consequence, the interfacial solvation structures and hydrogen bonding environments are dynamically tuned by the varying water dissociation capabilities across facets. This work elucidates how water dissociation energetics depend on surface orientation and interfacial structure, offering atomistic insights into manipulating reaction chemistry at electrocatalytic interfaces.
organic↗
Impact of disorder on dynamics and ordering in the honeycomb-lattice iridate Na 2 IrO 3
Kitaev's honeycomb spin-liquid model and its proposed realization in materials such as α-RuCl 3 , Li 2 IrO 3 , and Na 2 IrO 3 continue to present open questions about how the dynamics of a spin liquid are modified in the presence of non-Kitaev interactions as well as the presence of inhomogeneities. Here we use 23 Na nuclear magnetic resonance to probe both static and dynamical magnetic properties in single-crystal Na 2 IrO 3 . We find that the NMR shift follows the bulk susceptibility above 30 K but deviates from it below; moreover below T N the spectra show a broad distribution of internal magnetic fields. Both of these results provide evidence for inequivalent magnetic sites at low temperature, suggesting inhomogeneities are important for the magnetism. The spin-lattice relaxation rate is isotropic and diverges at T N , suggesting that the Kitaev cubic axes may control the critical quantum spin fluctuations. Finally, in the ordered state, we observe gapless excitations, which may arise from site substitution, emergent defects from milder disorder, or possibly be associated with nearby quantum paramagnetic states distinct from the Kitaev spin liquid.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Optical magnons with dominant bond-directional exchange interactions in the honeycomb lattice iridate α — Li 2 IrO 3
We have used resonant inelastic x-ray scattering to reveal optical magnons in a honeycomb lattice iridate α - Li 2 IrO 3 . The spectrum in the energy region 20–25 meV exhibits momentum dependence, of which energy is highest at the location of the magnetic Bragg peak, ( h , k ) = ( ± 0.32 , 0 ) , and lowered toward ( 0 , 0 ) and ( ± 1 , 0 ) . We compare our data with a linear spin-wave theory based on a generic nearest-neighbor spin model. We find that a dominant bond-directional Kitaev interaction of order 20 meV is required to explain the energy scale observed in our study. The observed excitations are understood as stemming from optical magnon modes whose intensity is modulated by a structure factor, resulting in the apparent momentum dependence. We also observed diffuse magnetic scattering arising from the short-range magnetic correlation well above T N . In contrast to Na 2 IrO 3 , this diffuse scattering lacks the C 3 rotational symmetry of the honeycomb lattice, suggesting that the bond anisotropy is far from negligible in α - Li 2 IrO 3 .
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Complex pressure-temperature structural phase diagram of the honeycomb iridate Cu 2 IrO 3
Cu 2 IrO 3 is among the newest layered honeycomb iridates and a promising candidate to harbor a Kitaev quantum spin liquid state. Here, we investigate the pressure and temperature dependence of its structure through a combination of powder x-ray diffraction and x-ray absorption fine structure measurements, as well as ab initio evolutionary structure search. At ambient pressure, we revise the previously proposed C2/c solution with a related but notably more stable P2 1 /c structure. Pressures below 8 GPa drive the formation of Ir-Ir dimers at both ambient and low temperatures, similar to the case of Li 2 IrO 3 . At higher pressures, the structural evolution dramatically depends on temperature. Furthermore, a large discontinuous reduction of the Ir honeycomb interplanar distance is observed around 15 GPa at room temperature, likely driven by a collapse of the O-Cu-O dumbbell bonds. At 15 K, pressures beyond 20 GPa first lead to an intermediate phase featuring a continuous reduction of the interplanar distance, which then collapses at 30 GPa across yet another phase transition. However, the resulting structure around 40 GPa is not the same at room and low temperatures. Remarkably, the reduction in interplanar distance leads to an apparent healing of the stacking faults at room temperature, but not at 15 K. Possible implications on the evolution of electronic structure of Cu 2 IrO 3 with pressure are discussed.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Exploring magnetic anisotropy and robustness of the J eff = 1/2 state under substantial orthorhombic distortion in Sr 2 IrO 4 thin films
Here, we present a comprehensive study revealing the intricate interplay of the magnetic anisotropy and orthorhombic distortion in thin films of Sr 2 IrO 4 through a Ca 3 Ru 2 O 7 substrate. By inducing a pronounced orthorhombic distortion along the direction of oxygen octahedral edges, we effectively modulated the uniaxial magnetic anisotropy in the system. Remarkably divergent responses along the easy and hard magnetic axes were unveiled through x-ray magnetic circular dichroism (XMCD) measurements under magnetic fields. Specifically, the spin flop transition observed when the magnetic field aligns with the hard axis allows us to estimate the magnetic anisotropy energy, which is around 14.2 µeV, close to that estimated from the single magnon peak measured via Raman spectroscopy. The observed anisotropy energy remains notably lower than the linear estimates derived from the strain-anisotropy energy relationship outlined in H.-H. Kim et al., Nat. Commun. 13, 6674 (2022). This underscores the enduring preservation of the isotropic character of the J eff = 1/2 states. This is also supported by the negligible XMCD intensity ratio at the L 2 edge compared to that of the L 3 edge. Furthermore, the branching ratio determined from x-ray absorption spectroscopy shows that the expectation value of the spin-orbit coupling is similar to that of bulk Sr 2 IrO 4 single crystals. Our findings indicate that even under a substantial anisotropic biaxial distortion, Sr 2 IrO 4 remains remarkably proximate to the J eff = 1/2 state. This study not only provides valuable information in understanding the interplay between magnetic anisotropy and strain but also the robustness of the J eff = 1/2 state under octahedral distortion within materials exhibiting emergent quantum phenomena.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗