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Applicability of iridium as protective coating for refractory metals - rates of interdiffusion of iridium with tungsten, molybdenum, and niobium
Spin-orbit-coupled Mott iridates show great similarity with parent compounds of superconducting cuprates, attracting extensive research interest especially for their electron-doped states. However, previous experiments have been largely limited within a small doping range due to the absence of effective dopants, and therefore the electron-doped phase diagram remains elusive. Here, an ionic-liquid-gating-induced protonation method is utilized to achieve electron-doping into a 5d Mott-insulator built with a SrIrO 3 /SrTiO 3 superlattice (SL), and a systematic mapping of its electron-doped phase diagram is achieved with the evolution of the iridium valence state from 4+ to 3+, equivalent to doping of one electron per iridium ion. Along increasing doping level, the parent Mott-insulator is first turned into a localized metallic state with gradually suppressed magnetic ordering, and then further evolves into a nonmagnetic band insulating state. This work forms an important step forward for the study of electron-doped Mott iridate systems, and the strategy of manipulating the band filling in an artificially designed SL structure can be readily extended into other systems with more exotic states to explore.
Instrumentation to provide process monitoring (PM) and safeguards for the oxide reduction (OR) step in the electrochemical processing of used oxide nuclear fuel is necessary to ensure equipment is operated as declared. Cyclic voltammetry (CV) has been proposed for real-time monitoring of the operation of an OR process for safeguards purposes. In this study, different materials including 316 stainless steel (SS), tantalum (Ta), molybdenum (Mo), tungsten (W), platinum (Pt), and iridium (Ir) were evaluated as potential working electrode (WE) materials based on their chemical inertness, corrosion resistance, and sensitivity in detecting Li 2 O and other chloride salts in the OR electrolyte. Of the electrodes evaluated, 316 SS, Ir, and Pt all performed reasonably well in the LiCl-Li 2 O electrolyte. Here, stainless steel was operated in the cathodic potential and had reasonable corrosion resistance and is relatively inexpensive. Iridium could be operated in both the cathodic and anodic potentials and was the most corrosion resistant of those evaluated. Platinum is limited to the anodic potential range, had reasonable corrosion resistance, and was the most sensitive to Li 2 O concentrations in the salt. In the development of a stand-alone safeguards instrumentation, our recommendation is a CV sensor fitted with both Ir and Pt WEs. The results in this study may also be helpful for anode material selection in other electrometallurgy industries, such as molten salt electrolysis.
In this work, the combined use of reaction kinetic analysis, ultrafast spectroscopy, and stoichiometric organometallic studies has enabled the elucidation of the mechanistic underpinnings to a photocatalytic C–N cross-coupling reaction. Steady-state and ultrafast spectroscopic techniques were used to track the excited-state evolution of the employed iridium photocatalyst, determine the resting states of both iridium and nickel catalysts, and uncover the photochemical mechanism for reductive activation of the nickel cocatalyst. Stoichiometric organometallic studies along with a comprehensive kinetic study of the reaction, including rate–driving force analysis, unveiled the crucial role of photocatalysis in both initiating and sustaining a Ni(I)/Ni(III) cross-coupling mechanism. The insights gleaned from this study further enabled the discovery of a new photocatalyst providing a >30-fold rate increase.
The development of electrocatalysts with reduced iridium (Ir) loading for the oxygen evolution reaction (OER) is essential to produce low-cost green hydrogen from water electrolysis under acidic conditions. Herein, an atomically thin layer of iridium oxide (IrO x ) has been uniformly dispersed onto cobalt oxide (Co 3 O 4 ) nanocrystals to improve the efficient use of Ir for acidic OER. In situ characterization and theoretical calculations reveal that compared to the conventional IrOx cluster, the atomically thin layer of IrO x shows stronger interaction with the Co 3 O 4 and consequently higher OER activity due to the Ir-O-Co bond formation at the interface. Equally important, the facile synthetic method and the promising activity in the proton exchange membrane water electrolyzer, reaching 1 A cm -2 at 1.7 V with remarkable durability, enable potential scale-up applications. In conclusion, these findings provide a mechanistic understanding for designing active, stable and lower-cost electrocatalysts with well-defined structures for acidic OER.
The synthesis of weak chemical bonds at or near thermodynamic potential is a fundamental challenge in chemistry, with applications ranging from catalysis to biology to energy science. Proton-coupled electron transfer using molecular hydrogen is an attractive strategy for synthesizing weak element–hydrogen bonds, but the intrinsic thermodynamics presents a challenge for reactivity. Here we describe the direct photocatalytic synthesis of extremely weak element–hydrogen bonds of metal amido and metal imido complexes, as well as organic compounds with bond dissociation free energies as low as 31 kcal mol –1 . Key to this approach is the bifunctional behaviour of the chromophoric iridium hydride photocatalyst. Activation of molecular hydrogen occurs in the ground state and the resulting iridium hydride harvests visible light to enable spontaneous formation of weak chemical bonds near thermodynamic potential with no by-products. In conclusion, photophysical and mechanistic studies corroborate radical-based reaction pathways and highlight the uniqueness of this photodriven approach in promoting new catalytic chemistr
Although metal complexes are known to split dinitrogen at ambient temperature and pressure, the synthesis of ammonia from these compounds and using H 2 as the terminal reductant has been rarely achieved. Here, we report photocatalytic ammonia synthesis from a N 2 -derived terminal molybdenum nitride and by using H 2 as the terminal reductant. An iridium hydride photocatalyst mediates the reaction upon irradiation with blue light. A molybdenum pentahydride was identified as the principal metal product arising following ammonia release. Conversion of the molybdenum pentahydride back to the terminal molybdenum nitride was accomplished in three-steps and completes a synthetic cycle for NH3 formation from N 2 and H 2 . Mechanistic investigations support a pathway involving photoexcitation of the iridium hydride and subsequent energy transfer rather than electron transfer. Deuterium labelling confirmed H 2 as the source of the N–H bonds. This photodriven, proton coupled electron transfer allows the use of H 2 as the terminal reductant for catalytic formation of NH 3 from N 2 using metal catalysts.
Due to the rapidly developing technologies and huge market demand, there has been increasing interest internationally in exploring permanent magnet formulations in addition to the well-known Nd 2 Fe 14 B and SmCo 5 /Sm 2 Co 17 . Given Fe's low materials cost and generally high magnetization, Fe-rich rare earth binaries such as Ce 2 Fe 17 comprise a rich “hunting ground” for such new materials. While this compound suffers from a low ordering point and is a heli magnet, these difficulties are easily remedied by the substitution of appropriate amounts of cobalt for Fe, with room-temperature saturation magnetization as high as 1.5 T. In this work, we try to switch the all-important magnetic anisotropy from planar to uniaxial behavior in Ce 2 Fe 17 via 18 h - and 6 c -type atom substitutions with Si, Ir, and numerous other atoms. The uniaxial magnetocrystalline anisotropy is successfully achieved in the 6 c -site-substituted Ce 2 Fe 15 Ir 2 systems, along with large magnetization. We find that iridium substitution, in particular, induces a substantial uniaxial anisotropy of 11.25 MJ/m 3 , which is comparable to most of the current rare earth permanent magnets. Although the iridium substitution is costly, the finding of Ir-triggered uniaxial magnetic anisotropy indicates the potential of Ce–Fe-based alloys for permanent magnets.
The 5d pyrochlore iridate family (R 2 Ir 2 O 7 , where R is a rare earth ion) has garnered significant attention due to its topological properties, such as Weyl semimetallic phases and axion insulator. However, the investigation of these properties has been impeded by severe iridium loss during growth, which results in the formation of defects and impurities. Herein, we demonstrate a method for controlling impurities and defects in strained Nd 2 Ir 2 O 7 (NIO-227) films by compensating for iridium loss during growth. By increasing the amount of IrO 2 target ablated, we enhance the morphological quality and electrical transport properties of the fabricated films. Furthermore, our results show that the anomalous Hall effects of the films have a strong dependency on the amount of IrO 2 target ablated, which is attributed to the structural inhomogeneity in the NIO-227 films. Our work provides a way to control defects and impurities and would promote the investigation of topological phases in the family R 2 Ir 2 O 7 .
This study explores the effect of molecular permanent dipole moment (PDM) on aggregation of guest molecules in phosphorescent host–guest organic light-emitting diodes (OLEDs). Through a combination of photoluminescence measurements, high-angle annular dark-field scanning transmission electron microscopy analysis, and an Ising model based physical vapor-deposition simulation, we show that higher PDM of tris[2-phenylpyridinato-C2,N]iridium(III) guest can actually lead to a reduced aggregation relative to tris[bis[2-(2-pyridinyl-N)phenyl-C] (acetylacetonato)iridium(III) when doped into a non-polar host 1,3,5-tris(carbazol-9-yl)benzene. This study further explores the effect of host polarity by using a polar host 3′,5′-di(carbazol-9-yl)-[1,1′-biphenyl]-3,5-dicarbonitrile, and it is shown that the polar host leads to reduced guest aggregation. In conclusion, this study provides a comprehensive understanding of the impact of molecular PDM on OLED material efficiency and stability, providing insights for optimizing phosphorescent OLED materials.
Iridium-based oxygen evolution catalysts are screened in this study for activity and stability with rotating disk electrode (RDE) half-cells. This study focuses on the electrochemical and materials approaches needed to characterize oxygen evolution catalysts, and include testing for activity, stability, composition, oxide content, and structure. Findings also discuss recommendations for data interpretation and detail the difficulties of comparing catalysts across materials sets with different elemental and oxide compositions, and linking RDE activity to device-level performance. The materials evaluated are a mixture of oxides and metals, and several methods are used to quantify metal content, qualitatively assess oxide content, and determine total surface area. Oxygen evolution activities and stabilities are compared, where a wide range of results are reported. In general, higher RDE performances are found for catalysts that contained larger amounts of ruthenium and metals. Higher durability, however, is found for catalysts that only contained iridium and a higher proportion of oxides. Additionally, catalysts are evaluated for performance in membrane electrode assemblies to assess RDE as a predictive tool in electrolysis. While activity trends within individual material sets generally held between ex- and in-situ testing, RDE tends to overestimate the activity of more metallic catalysts when compared to device-level performance. These results stress the need for multiple metal/oxide baselines for mixed catalysts, to better project in-situ kinetics.
Device-level stress tests are developed that focus on anode catalyst layer degradation and future anticipated operating conditions, including intermittent load and reduced platinum group metal content. Square-wave cycles with an upper load limit of 2.5 A cm -2 are utilized to screen commercial iridium (Ir) materials. Performance losses are primarily due to decreasing kinetics and are accompanied by catalyst migration into the membrane, worsening catalyst/ionomer integration, and weakening of the catalyst/membrane interface. For ruthenium-containing catalysts, the in situ performances are higher but durabilities lower than Ir baselines, and any performance advantage is lost within the test. Increased loss is likely due to the higher dissolution rate; microscopy confirmed greater degrees of ruthenium migration. For Ir metal or mixed oxides, ex situ activity improvements generally did not translate to in situ performance. The durability, however, is significantly lower and the loss rate increased from 3 (oxide) to 9 (metal) μ V cycle -1 . These results are consistent with historical findings in literature, rationalize the continued use of iridium oxide as a baseline catalyst, and demonstrate that traditional catalyst development approaches may not improve device-level durability when focused on low-cost applications. A shift in focus may therefore be more effective at improving catalyst utilization and lessening load requirements.
Stress tests are developed that focus on anode catalyst layer degradation in proton exchange membrane electrolysis due to simulated start-stop operation. Ex situ testing indicates that repeated redox cycling accelerates catalyst dissolution, due to near-surface reduction and the higher dissolution kinetics of metals when cycling to high potentials. Similar results occur in situ, where a large decrease in cell kinetics (>70%) is found along with iridium migrating from the anode catalyst layer into the membrane. Additional processes are observed, however, including changes in iridium oxidation, the formation of thinner and denser catalyst layers, and platinum migration from the transport layer. Increased interfacial weakening is also found, adding to both ohmic and kinetic loss by adding contact resistances and isolating portions of the catalyst layer. Repeated shutoffs of the water flow further accelerate performance loss and increase the frequency of tearing and delamination at interfaces and within catalyst layers. These tests were applied to several commercial catalysts, where higher loss rates were observed for catalysts that contained ruthenium or high metal content. These results demonstrate the need to understand how operational stops occur, to identify how loss mechanisms are accelerated, and to develop strategies to limit performance loss.
One of the main degradation mechanisms of hydrous iridium oxide acidic oxygen evolution reaction (OER) catalysts is dissolution and loss into the acidic membrane. While degradation models have been proposed, there is a gap in understanding the potential and time dependence of the iridium dissolution reaction and its mechanistic underpinnings. In this work, Ir dissolution rates measured as a function of time and potential via time-resolved inductively-coupled plasma mass spectrometry (ICP-MS) in aqueous acidic electrolyte are used to establish a mathematical model for Ir dissolution. The mathematical model is generated using proposed formation and dissolution reactions for Ir species. Through comparison with the ICP-MS data and existing information on the potential-dependent Ir phase, we find that the potential and time-dependence of dissolution can be modeled as dissolution of an oxide phase, here represented as IrO 2 , with potential dependent kinetics and formation of a passivating species, a process with a rate-limiting step that is not potential dependent. This understanding of the potential dependence of dissolution and passivation kinetics using aqueous electrolyte half-cell measurements can be used to predict the degradation of Ir oxide in operating energy conversion devices relying on the OER, such as proton-exchange membrane water electrolyzers.
Roundness (or circularity) and flatness measurements are made as part of the dimensional inspection process to certify that iridium alloy Clad Vent Set (CVS) cups meet the dimensional requirements of Iridium Alloy Cup Drawing M2D920101A005, Rev. 4 (see Figure 1). A Mahr Federal (Providence, RI) MarForm MMQ 400 Formtester is specified in the cup inspection Procedure GPHS-C-3624/25, Rev. 25 for roundness (dimension 16) and flatness (dimension 17). The Mahr Federal (Providence, RI) MarForm MMQ 400 Formtester stopped functioning in 2019. A new Mitutoyo RA-2200 Roundness Tester was purchased to replace the MMQ 400. Evaluations were conducted to qualify the new RA-2200 for CVS cup dimensional inspection work. The criterion for qualification was to ensure that the new RA-2200 instrument would yield roundness and flatness inspection results equivalent to or better than the predecessor MMQ 400 instrument.
Solar energy applications rely heavily on p-block elements and transition metals. Silicon is, by far, the most commonly used material in photovoltaic cells and accounts for about 85% of modules sold presently. Of late, thin film photovoltaic cells have gained momentum because of their higher efficiencies. Most of these thin film devices are made out of just five elements, namely, cadmium, tellurium, selenium, indium, gallium and copper. The present manuscript describes an elegant and inexpensive molten salt-based electrolytic process for fabricating a tellurium-coated metallic substrate. A three-electrode set up was employed to coat iridium with tellurium from a molten bath containing lithium chloride, lithium oxide and tellurium tetrachloride (LiCl-Li 2 O-TeCl 4 ) at 650 °C for a duration ranging from 30 to 120 min under a galvanostatic mode. The tellurium coating was observed to be thick, uniform, smooth and homogeneous. Additionally, the deposited tellurium did not chemically react with the iridium substrate to form intermetallic compounds, which is a good feature from the standpoint of the device’s performance characteristics. The present process, being generic in nature, shows the potential for the manufacture of both the coated substates and high-purity elements not just for tellurium but also for other p-block elements.
Various refractory coating systems were evaluated for rocket nozzle applications by actual rocket test firings. A reference is noted which identifies failure mechanisms and gives results of the firing tests for 18 coating systems. Iridium, iridium-rhenium, and hafnium oxide-zirconium oxide coatings show most promising results.
An evaluation is presented of silicon carbide, zirconium diboride, and iridium-coated graphite as materials for construction of furnace cores which could operate under highly oxidizing conditions at temperatures of approximately 2,200 C in the presence of molten aluminum oxide. It was found that silicon carbide and zirconium diboride could not withstand oxidizing atmospheres in the presence of aluminum oxide at temperature 2,200 C. However, graphite furnace cores coated with iridium were found to be useful furnace cores at 2,200 C in an oxidizing atmosphere for reasonably extended periods of time.