SEARCH · Engineering Papers
Results for “Ir”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Comprehensive Mechanisms of Electrocatalytic CO2 Reduction by [Ir(bip)(ppy)(CH3CN)](PF6)2
Explore the source record for details and available documents.
Electronic properties of corundum-like Ir 2 O 3 and Ir 2 O 3 -Ga 2 O 3 alloys
In the hexagonal, corundum-like structure, α-Ga 2 O 3 has a bandgap of ~5.1 eV, which, combined with its relatively small electron effective mass, high Baliga's figure of merit, and high breakdown field, makes it a promising candidate for power electronics. Ga 2 O 3 is easy to dope n-type, but impossible to dope p-type, impeding the realization of some electronic device designs. Developing a lattice-matched p-type material that forms a high-quality heterojunction with n-type Ga 2 O 3 would open new opportunities in electronics and perhaps optoelectronic devices. In this work, we studied Ir 2 O 3 as a candidate for that purpose. Using hybrid density functional theory calculations we predict the electronic band structure of α-Ir 2 O 3 and compare that to α-Ga 2 O 3 , and study the stability and electronic properties of α-(Ir x Ga 1–x ) 2 O 3 alloys. We discuss the band offset between the two materials and compare it with recently available experimental data. We find that the Ir d bands that compose the top of the valence band in α-Ir 2 O 3 are much higher in energy than O p bands in α-Ga 2 O 3 , possibly enabling effective p-type doping. Finally, our results provide an insight into using the Ir 2 O 3 or Ir 2 O 3 -Ga 2 O 3 alloys as p-type material lattice-matched to α-Ga 2 O 3 for the realization of p–n heterojunctions.
Two micron observations of C-12O and C-13O in the red giant sources IRS 7, IRS 12, and IRS 19
Explore the source record for details and available documents.
AFM-IR and s-SNOM-IR measurements of chemically addressable monolayers on Au nanoparticles
The performance of catalysts depends on their nanoscale properties, and local variations in structure and composition can have a dramatic impact on the catalytic reactivity. Therefore, probing the localized reactivity of catalytic surfaces using high spatial resolution vibrational spectroscopy, such as infrared (IR) nanospectroscopy and tip-enhanced Raman spectroscopy, is essential for mapping their reactivity pattern. Two fundamentally different scanning probe IR nanospectroscopy techniques, namely, scattering-type scanning near-field optical microscopy (sSNOM) and atomic force microscopy-infrared spectroscopy (AFM-IR), provide the capabilities for mapping the reactivity pattern of catalytic surfaces with a spatial resolution of ~20 nm. Herein, we compare these two techniques with regard to their applicability for probing the vibrational signature of reactive molecules on catalytic nanoparticles. For this purpose, we use chemically addressable self-assembled molecules on Au nanoparticles as model systems. We identified significant spectral differences depending on the measurement technique, which originate from the fundamentally different working principles of the applied methods. While AFM-IR spectra provided information from all the molecules that were positioned underneath the tip, the s-SNOM spectra were more orientation-sensitive. Due to its field-enhancement factor, the s-SNOM spectra showed higher vibrational signals for dipoles that were perpendicularly oriented to the surface. The s-SNOM sensitivity to the molecular orientation influenced the amplitude, position, and signal-to-noise ratio of the collected spectra. Ensemble-based IR measurements verified that differences in the localized IR spectra stem from the enhanced sensitivity of s-SNOM measurements to the adsorption geometry of the probed molecules.
Determining the 193 m Ir/ 192 Ir ratio from high-resolution X-ray measurements
Two pellets of iridium salt were irradiated at the center of the Flattop critical assembly, one at low neutron flux and the other at high flux. After that two counting samples were prepared from each pellet following a given chemical procedure. Measurements of the four counting samples were carried out with two high-resolution silicon drift detectors for over a year. Pulse height spectra of the L→M X-rays from 193 m Ir and 192 Ir were approximated with a Voigt function and the ratio of produced 193 m Ir and 192 Ir nuclei obtained. The 193 m Ir/ 192 Ir ratios from each measured spectrum are compared to identify possible systematic deviations.
Ames-2021 CO 2 Dipole Moment Surface and IR Line Lists: Toward 0.1% Uncertainty for CO 2 IR Intensities
A highly accurate CO 2 ab initio dipole moment surface (DMS), Ames-2021, is reported along with 12 C 16 O 2 infrared (IR) intensity comparisons approaching a 1–4‰ level of agreement and uncertainty. The Ames-2021 DMS was accurately fitted from CCSD(T) finite-field dipoles computed with the aug-cc-pVXZ (X = T, Q, 5) basis for C atom and the d-aug-cc-pVXZ (X = T, Q, 5) basis for O atoms, and extrapolated to the one particle basis set limit. Fitting σ(rms) is 3.8 × 10^(–7) au for 4443 geometries below 15 000 per cm . The corresponding IR intensity, S Ames-2021 , are computed using the Ames-2 potential energy surface (PES), which is the best PES available for CO 2 . Compared to high accuracy IR studies for 2001i–00001 and 3001i–00001 bands, S Ames-2021 matches NIST experiment-based intensities [S NIST-HIT16 or S HIT20 ] to −1.0 ± 1.3‰, or matches DLR experiment-based intensities [S DLR-HIT16/UCL/Ames ] to 1.9 ± 3.7‰. This indicates the systematic deviations and uncertainties have been significantly reduced in S Ames-2021 . The S UCL2015 (or S HITRAN2016 ) have larger deviations (vs S DLR ) and uncertainties (vs S DLR , S NIST ) which are attributed to the less accurate Ames-1 PES adopted in UCL-296 line list calculation. The S Ames-2021 intensity of 12 C 16 O 2 and 13 C 16 O 2 is utilized to derive new absolute 13 C/ 12 C ratios for Vienna PeeDee Belemnite (VPDB) with uncertainty reduced by 1/3 or 2/3. Further evaluation of S Ames-2021 are carried out on those CO 2 bands discussed in the HITRAN2020 update paper. Consistent improvements and better accuracies are found in band-by-band analysis, except for those bands strongly affected by Coriolis couplings, or very weak bands measured with relatively larger experimental uncertainties. The Ames-2021 296 K IR line lists are generated for 13 CO 2 isotopologues, with 18,000 per and S 296K > 1E–31) cm/molecule cutoff and then combined with CDSD line positions (except 14 C 16 O 2 ). The Ames-2021 DMS and 296 K IR line lists represent a major improvement over previous CO 2 theoretical IR intensity studies, including Ames-2016, UCL-296, and recent UCL DMS 2021 update. A real 1 permille level of agreement and uncertainty will definitely require both more accurate PES and more accurate DMS.
Mathematical Modeling of the Potential and Time Dependence of Ir Dissolution from Hydrous Ir Oxide Oxygen Evolution Catalysts
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.
High-Resolution X-ray Photoelectron Spectroscopy of an IrO2(110) Film on Ir(100)
Explore the source record for details and available documents.
Nonlinear post-compression in multi-pass cells in the mid-IR region using bulk materials
We numerically investigate the regime of nonlinear pulse compression at mid-IR wavelengths in a multi-pass cell (MPC) containing a dielectric plate. This post-compression setup allows for ionization-free spectral broadening and self-compression while mitigating self-focusing effects. We find that self-compression occurs for a wide range of MPC and pulse parameters and derive scaling rules that enable its optimization. We also reveal the solitonic dynamics of the pulse propagation in the MPC and its limitations and show that spatiotemporal/spectral couplings can be mitigated for appropriately chosen parameters. In addition, we reveal the formation of spectral features akin to quasi-phase matched degenerate four-wave mixing. Finally, we present two case studies of self-compression at 3-μm and 6-μm wavelengths using pulse parameters compatible with driving high-field physics experiments. The simulations presented in this paper set a framework for future experimental work using few-cycle pulses at mid-IR wavelengths.
Short-range ferromagnetic order due to Ir substitutions in single-crystalline Ba(Co 1-x Ir x ) 2 As 2 (0 ≤ x ≤ 0.25)
The ternary-arsenide compound BaCo 2 As 2 was previously proposed to be in proximity to a quantum-critical point where long-range ferromagnetic (FM) order is suppressed by quantum fluctuations. In this paper we report the effect of Ir substitutions for Co on the magnetic and thermal properties of Ba(Co 1-x Ir x ) 2 As 2 (0 ≤ x ≤ 0.25) single crystals. These compositions all crystallize in an uncollapsed body-centered-tetragonal ThCr 2 Si 2 structure with space group I4/mmm. Magnetic susceptibility measurements reveal clear signatures of short-range FM ordering for x ≥ 0.11 below a nearly composition-independent characteristic temperature T cl ≈ 13 K. The small variation of T cl with x, thermomagnetic irreversibility between zero-field-cooled and field-cooled magnetic susceptibility versus T, the occurrence of hysteresis in magnetization versus field isotherms at low field and temperature, and very small spontaneous and remanent magnetizations <0.01 μ B /f.u. together indicate that the FM response arises from short-range FM ordering of FM spin clusters as previously inferred to occur in Ca(Co 1–x Ir x ) 2–y As 2 . Heat-capacity Cp(T) data do not exhibit any clear feature around Tcl, consistent with the very small moments of the FM clusters. The Cp(T) in the paramagnetic temperature regime 25–300 K is well described by the sum of a Sommerfeld electronic contribution and Debye and Einstein lattice contributions where the latter lattice contribution suggests the presence of low-frequency optic modes associated with the heavy Ba atoms in the crystals.
Correlation between antiferromagnetic and Mott states in spin orbit coupled Sr 2 Ir O 4 : A study of Sr 2 Ir 1 – x M x O 4 ( M = Fe or Co)
Sr 2 IrO 4 is an archetypal spin-orbit-coupled Mott insulator with an antiferromagnetic state below 240 K. Here we report results of our study on single crystals of Sr 2 Ir 1–x Fe x O 4 (0 ≤ x < 0.32) and Sr 2 Ir 1–x Co x O 4 (0 ≤ x < 0.22). Fe doping retains the antiferromagnetic state but simultaneously precipitates an emergent metallic state whereas Co doping causes a rapid collapse of both the antiferromagnetic and Mott states, giving rise to a confined metallic state featuring a pronounced linearity of the basal-plane resistivity up to 700 K. The results indicate tetravalent Fe 4+ (3d 4 ) ions in the intermediate spin state with S = 1 and Co 4+ (3d 5 ) ions in the high spin state with S = 5/2 substituting for Ir 4+ (5d 5 ) ions in Sr 2 IrO 4 , respectively. The effective magnetic moment closely tracks the Néel temperature as doping increases, suggesting that the spin state of the dopant predominately determines the magnetic properties in doped Sr 2 IrO 4 . Furthermore, all relevant properties including charge-carrier density (e.g., 10 28 /m 3 ), Sommerfeld coefficient (e.g., 19 mJ / mole K 2 ), and Wilson ratio (e.g., 2.6) consistently demonstrate an emergent metallic state that is both robust and highly correlated in the two systems, arising from the percolation of bound states and the weakening of structural distortions. Furthermore, this study strongly indicates that the antiferromagnetic and Mott states are correlated in an unconventional manner in Sr 2 IrO 4 .
Optical alignment and testing of the Diffuse IR Background Experiment IR cryogenic telescope
Diffuse Infrared Background Experiment (DIRBE) optical alignment and testing methods are discussed. Using strobe videography, vibration and performance testing of a 32 hz tuning-fork chopper was carried out. The Cosmic Background explorer satellite provides improved microwave and IR all-sky maps of the cosmic background radiation from a polar orbit. A liquid helium cryostat houses the DIRBE and the Far IR Absolute Spectrophotometer (FIRAS) instruments at a temperature of 2 K. Differential MicRowave Radiometers (DMRs) provide large scale maps of anisotropy of the 3 K background at wavelengths of 3.3, 5.7, and 9.6 mm. The DIRBE telescope is an IR photometric instrument with 10 wavelength bands between 1 and 300 microns, designed to measure radiation from the epoch of galaxy formation. Stringent stray light requirements mean that the DIRBE flight instrument has to be built and tested in a class 100 environment.
IDENTIFICATION OF ADSORBA TION OF ADSORBATE FT-IR BANDS USING IN-SI -IR BANDS USING IN-SITU TECHNIQUES: Pd SPECIATION AND ADSORPTION CHEMISTRY OF Pd-ZEOLITES FOR PASSIVE NOx ADSORPTION
To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NOx) once the catalyst reaches operational temperature (~200 °C). NOx emitted at lower catalyst temperatures now comprises most of the NOx released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NOx adsorbers present an appealing solution to the cold start problem, these being a class of materials that chemisorb exhaust components such as NOx, carbon monoxide (CO) and hydrocarbons at near-ambient temperatures, and then desorb these compounds once the downstream catalyst has reached operational temperature. An effective passive NOx adsorber must have several properties: high NOx adsorption at near-ambient temperatures, near-complete NOx desorption at temperatures within the operational range, high thermal stability, and resistance to automotive exhaust components at high temperatures. The potential environmental impact of such a system is substantial, as NOx emissions currently result in the formation of millions of tons of smog and acid rain each year. Pd-exchanged zeolites have shown promise for deployment as Passive NOx adsorbers, though much remains to be understood about their adsorption chemistry and deactivation. In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) provides a convenient probe of adsorbed species, most automotive exhaust components possessing IR-active chemical bonds. By examining the evolution of IR bands under various pretreatments and adsorbates, the overall Pd-speciation and adsorptive zeolite sites of each material can be characterized, and the identities of IR bands can be deduced. In this work, microreactor-MS analysis of the adsorption and desorption behavior of these materials was also examined, these results being coupled with in-situ DRIFTS temperature programmed desorption (TPD) to correlate desorption events with specific adsorbed species. A pair of zeolite frameworks of similar Si/Al ratio but differing pore size were examined, Beta zeolite (BEA) and Chabazite (CHA) representing a medium- and small-pore framework, respectively. The effect of Pd-loading on BEA was examined, as well as the various deactivation pathways and active sites of each material.
Characterization of Two Positional Isomers of the Cs + Gly Complex Using Two-Color, IR–IR Photobleaching of the Cryogenically Cooled Ions
Metal ion binding to amino acid residues is an important interaction motif that controls the tertiary structures of oligopeptides. Analyses of the vibrational band patterns displayed by the amino acid scaffolds are commonly used to characterize the local docking motifs. Here we carry out two-color, IR-IR photobleaching measurements to obtain isomer-selective vibrational spectra of the Cs + Gly ion-molecule complex isolated in a cryogenically cooled, radiofrequency ion trap. The distinct band patterns of two non-interconverting isomers are observed and traced to different bidentate binding motifs between Cs + and the glycine scaffold. In one isomer, the ion attaches to the oxygen atoms of the carboxyl group whereas in the other it docks to the amino nitrogen and the carbonyl oxygen. Attachment to the acid head group yields a very diffuse absorption associated the OH group engaged in a strong intramolecular H-bond that closes a 5 membered ring. Furthermore, the band assignments, rearrangement pathways and electrostatic distortion of the electron density distributions in the glycine scaffold by the proximal ion are explored with electronic structure calculations and anharmonic theory.
A novel method for measuring ultra-trace levels of U and Th in Au, Pt, Ir, and W matrices using ICP-QQQ-MS employing an O 2 reaction gas
A mass shift method using ICP-MS/MS with O 2 reaction gas is used for ultra-trace determinations of U and Th in samples containing W, Ir, Pt, and Au derived polyatomic interferants without the need for extensive chemical sample preprocessing.
One-step production of renewable adipic acid esters from mucic acid over an Ir–ReO x /C catalyst with low Ir loading
The production of adipic acid, a large-volume platform chemical, from biomass represents a petroleum-free route to manufacturing nylon and other polymers more sustainably. In this study, a one-step conversion of bioderived mucic acid to adipates is reported over a heterogeneous, bifunctional Ir–ReO x /C catalyst via deoxydehydration (DODH) and catalytic transfer hydrogenation (CTH) using isopropanol as a green solvent and reductant. With very low Ir content (0.05 wt%), the catalyst provides a low-cost option for the tandem DODH–CTH process, while still enabling reuse and regeneration for at least five cycles. The reported catalytic system generates adipates in good yield (63%) without the need for additives (acids or halogens) or high pressure H 2 . Through model reactions and spectroscopic analyses, a bifunctional DODH–CTH mechanism was supported, with the Re VI/IV redox pair as the active DODH species and Ir0 saturating the dialkene intermediate via CTH. Thermal treatment in catalyst preparation and regeneration was optimized to limit metal leaching while maintaining good activity. Further, the present work outlines a one-step deoxygenation of an aldaric acid substrate from biomass using a bimetallic catalyst of low noble metal content to an important monomer for the polymer industry. This system facilitates use in future syntheses of sustainable chemicals from renewable oxygenates where the catalyst is reusable and affordable.
Molecular hydrogen in the vicinity of NGC 7538 IRS 1 and IRS 2 - Temperature and ortho-to-para ratio
Near-infrared spectroscopic observations of the active star-forming region near NGC 7538 IRS 1 and IRS 2 were made. The relative intensities of the v = 1-0 Q(1), Q(3), and Q(5) lines of molecular hydrogen are used to calculate a rotational excitation temperature. Comparison of the measured intensity of the Q(2) transition relative to the intensity of Q(1) and Q(3) permitted the retrieval of the ratio of ortho-to-para hydrogen. It is found that an ortho-to-para ratio of between 1.6 and 2.35 is needed to explain the Q-branch line intensity ratios, depending on the excitation model used. This range in ortho-to-para ratios implies a range of molecular hydrogen formation temperature of approximately 105 K to 140 K.