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DOE OSTI2024

Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor

Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2013

Theoretical and experimental studies of hydrogen adsorption and desorption on Ir surfaces

Here, we report adsorption and desorption of hydrogen on planar Ir(210) and faceted Ir(210), consisting of nanoscale {311} and (110) facets, by means of temperature programmed desorption (TPD) and density functional theory (DFT) in combination with the ab initio atomistic thermodynamics approach. TPD spectra show that only one H 2 peak is seen from planar Ir(210) at all coverages whereas a single H 2 peak is observed at around 440 K (F1) at fractional monolayer (ML) coverage and an additional H 2 peak appears at around 360 K (F2) at 1 ML coverage on faceted Ir(210), implying structure sensitivity in recombination and desorption of hydrogen on faceted Ir(210) versus planar Ir(210), but no evidence is found for size effects in recombination and desorption of hydrogen on faceted Ir(210) for average facet sizes of 5-14 nm. Calculations indicate that H prefers to bind at the two-fold short-bridge sites of the Ir surfaces. In addition, we studied the stability of the Ir surfaces in the presence of hydrogen at different H coverages through surface free energy plots as a function of the chemical potential, which is also converted to a temperature scale. Moreover, the calculations revealed the origin of the two TPD peaks of H 2 from faceted Ir(210): F1 from desorption of H 2 on {311} facets while F2 from desorption of H 2 on (110) facets.

1st-principles↗

DOE OSTI2013

A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface

We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75 ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir–C and Ir–Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Charge ordering in Ir dimers in the ground state of Ba 5 AlIr 2 O 11

It has been well established experimentally that the interplay of electronic correlations and spin-orbit interactions in Ir 4+ and Ir 5+ oxides results in insulating J eff = 1/2 and J eff = 0 ground states, respectively. However, in compounds where the structural dimerization of iridium ions is favorable, the direct Ir d-d hybridization can be significant and takes a key role. Here, in this study, we investigate the effects of direct Ir d-d hybridization in comparison with electronic correlations and spin-orbit coupling in Ba 5 AlIr 2 O 11 , a compound with Ir dimers. Using a combination of ab initio many-body wave-function quantum chemistry calculations and resonant inelastic x-ray scattering experiments, we elucidate the electronic structure of Ba 5 AlIr 2 O 11 . We find excellent agreement between the calculated and the measured spin-orbit excitations. Contrary to expectations, the analysis of the many-body wave function shows that the two Ir (Ir 4+ and Ir 5+ ) ions in the Ir 2 O 9 dimer unit in this compound preserve their local J eff character close to 1/2 and 0, respectively. The local point group symmetry at each of the Ir ions plays an important role, significantly limiting the direct d-d hybridization. Our results emphasize that minute details in the local crystal field environment can lead to dramatic differences in the electronic states in iridates and 5d oxides in general.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Electronic and structural response to pressure in the hyperkagome-lattice Na 3 Ir 3 O 8

Here, the hyper-kagome lattice iridate Na 3 Ir 3 O 8 , closely related to spin liquid candidate Na 4 Ir 3 O 8 , is unusual in that spin-orbit interactions acting on the 1/3-filled J eff = 1/2 state lead to a semimetallic ground state, in contrast to the conventional insulating Mott state stabilized by S-O interactions in the 1/2-filled J eff = 1/2 state of other iridates including Na 4 Ir 3 O 8 . We have studied the evolution of crystal structure, electronic structure, and transport in Na 3 Ir 3 O 8 under high pressure using x-ray diffraction, x-ray absorption near edge structure, and electrical resistance measurements in a diamond anvil cell. The study was augmented by the use of ab initio calculations, which provided insight into pressure-induced changes in crystal and electronic structure. We found that Na 3 Ir 3 O 8 transforms from a semimetal to an insulator under pressure, with an estimated energy gap that increases to about 130 meV at P similar to 9 GPa. At approximately 10 GPa, a cubic-to-monoclinic structural transition takes place between two insulating phases. This structural transition features a sizable volume collapse and a high-pressure phase characterized by apparent dimerization of Ir-Ir distances, wide dispersion of Ir-O-Ir bond angles, and an increase in the occupation of 5 d states. Although the energy gap is reduced in the high-pressure phase, insulating behavior remains to the highest pressures similar to 1 Mbar. The strongly pressure-dependent insulating gap shows a positive correlation with the expectation value of the angular part of the S-O interaction, < L • S >, which may indicate an active role of S-O interactions in stabilizing the insulating state that emerges in the compressed Na 3 Ir 3 O 8 structure.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Localized modes in the IR phase of QCD

Infrared (IR) dimension function d IR ( λ ) characterizes the space effectively utilized by QCD quarks at Dirac scale λ , and indirectly the space occupied by glue fields. It was proposed that its nonanalytic behavior in thermal reflects the separation of QCD system into an IR component and an independent bulk. Here we study the “plateau modes” in the IR component, whose dimensional properties were puzzling. Indeed, in the recent scenario of transition to IR phase, this low-dimensional plateau connects the Anderson-like mobility edge λ IR = 0 in Dirac spectrum with mobility edges ± λ A . For this structure to be truly Anderson-like, plateau modes have to be exponentially localized, implying that both the effective distances L eff ∝ L γ and the effective volumes V eff ∝ L d IR in these modes grow slower than any positive power of IR cutoff L . Although γ = 0 was confirmed in the plateau, it was found that d IR ≈ 1 . Here we apply the recently proposed technique to the problem. We conclude that a plateau mode of pure-glue QCD at UV cutoff a = 0.085 fm occupies a subvolume of IR dimension zero with probability at least 0.9999, substantiating this aspect of metal-to-critical scenario to a respective degree. Published by the American Physical Society 2024

Astronomy & Astrophysics↗

DOE OSTI2017

The MOSDEF Survey: Metallicity Dependence of PAH Emission at High Redshift and Implications for 24 μm Inferred IR Luminosities and Star Formation Rates at z ∼ 2

We present results on the variation of 7.7 μm polycyclic aromatic hydrocarbon (PAH) emission in galaxies spanning a wide range in metallicity at z ∼ 2. For this analysis, we use rest-frame optical spectra of 476 galaxies at 1.37 ≤ z ≤ 2.61 from the MOSFIRE Deep Evolution Field (MOSDEF) survey to infer metallicities and ionization states. Spitzer/MIPS 24 μm and Herschel/PACS 100 and 160 μm observations are used to derive rest-frame 7.7 μm luminosities (L{sub 7.7}) and total IR luminosities (L{sub IR}), respectively. We find significant trends between the ratio of L{sub 7.7} to L{sub IR} (and to dust-corrected star formation rate [SFR]) and both metallicity and [O iii]/[O ii] (O{sub 32}) emission line ratio. The latter is an empirical proxy for the ionization parameter. These trends indicate a paucity of PAH emission in low-metallicity environments with harder and more intense radiation fields. Additionally, L{sub 7.7}/L{sub IR} is significantly lower in the youngest quartile of our sample (ages of ≲500 Myr) compared to older galaxies, which may be a result of the delayed production of PAHs by AGB stars. The relative strength of L{sub 7.7} to L{sub IR} is also lower by a factor of ∼2 for galaxies with masses M{sub ∗}<10{sup 10} M{sub ⊙}, compared to the more massive ones. We demonstrate that commonly used conversions of L{sub 7.7} (or 24 μm flux density, f {sub 24}) to L{sub IR} underestimate the IR luminosity by more than a factor of 2 at M{sub ∗}∼10{sup 9.6--10.0} M{sub ⊙}. We adopt a mass-dependent conversion of L{sub 7.7} to L{sub IR} with L{sub 7.7}/L{sub IR} = 0.09 and 0.22 for M{sub ∗}⩽10{sup 10} and >10{sup 10} M{sub ⊙}, respectively. Based on the new scaling, the SFR–M {sub *} relation has a shallower slope than previously derived. Our results also suggest a higher IR luminosity density at z ∼ 2 than previously measured, corresponding to a ∼30% increase in the SFR density.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1979

Discovery of a compact far-infrared source, IR 12.4+0.5

Results are reported for far-IR, CO, 8-GHz, 15-GHz, H2O, and near-IR observations of a compact far-IR source (designated IR 12.4+0.5) in the M17 molecular cloud, as well as for CO and near-IR observations of a CO peak (designated MC 12.8+0.5) 24 arcmin to the NE of IR 12.4+0.5. The observed far-IR signal from IR 12.4+0.5 is found to correspond to a flux of 2400 Jy at 69 microns for a color temperature of 70 K, and the FWHM size of the source is estimated to be about 36 arcsec. The CO data for both sources and the observed reddening of background giants are shown to indicate high column densities; the existence of internal heat sources is inferred from the measured CO temperatures and the far-IR emission. It is concluded that the two sources are probably sites of very recent or ongoing star formation and that IR 12.4+0.5 is consistent with the 'cocoon star' model of early star formation.

Wright, E. L.↗

DOE OSTI2022

Photothermal Atomic Force Microscopy Coupled with Infrared Spectroscopy (AFM-IR) Analysis of High Extinction Coefficient Materials: A Case Study with Silica and Silicate Glasses

Photothermal atomic force microscopy coupled with infrared spectroscopy (AFM-IR) brings significant value as a spatially resolved surface analysis technique for disordered oxide materials such as glasses, but additional development and fundamental understanding of governing principles is needed to interpret AFM-IR spectra, since the existing theory described for organic materials does not work for materials with high extinction coefficients for infrared (IR) absorption. This paper describes theoretical calculation of a transient temperature profile inside the IR-absorbing material considering IR refraction at the interface as well as IR adsorption and heat transfer inside the sample. Furthermore, this calculation explains the differences in peak positions and amplitudes of AFM-IR spectra from those of specular reflectance and extinction coefficient spectra. It also addresses the information depth of the AFM-IR characterization of bulk materials. AFM-IR applied to silica and silicate glass surfaces has demonstrated novel capability of characterizing subsurface structural changes and surface heterogeneity due to mechanical stresses from physical contacts, as well as chemical alterations manifested in surface layers through aqueous corrosion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

CO 2 Hydrogenation and Formic Acid Dehydrogenation Using Ir Catalysts with Amide-Based Ligands

In this work, a series of Ir catalysts bearing amide-based ligands generated by a deprotonated amide moiety was prepared with the hypotheses that the strong electron-donating ability of the coordinated anionic nitrogen atom and the proton-responsive OH group near the metal center will improve the catalytic activity for CO 2 hydrogenation and formic acid (FA) dehydrogenation. The effects of the modifications of the ligand architecture on the catalytic activity were investigated for CO 2 hydrogenation at ambient conditions (25 °C with 0.1 MPa H 2 /CO 2 (v/v = 1/1)) and under slightly harsher conditions (50 °C with 1.0 MPa H 2 /CO 2 ) in basic aqueous solutions together with deuterium kinetic isotope effects (KIEs) with selected catalysts. Cp*Ir( L12 )(H 2 O)HSO 4 ( L12 = 6-hydroxy- N -phenylpicolinamidate) that has an anionic coordinating N atom and an OH group in the second coordination sphere, exhibits a turnover frequency (TOF) of 198 h –1 based on the initial 1 h of reaction. This TOF which, to the best of our knowledge, is the highest value ever reported under ambient conditions in basic aqueous solutions. However, Cp*Ir( L10 )(H 2 O)HSO 4 ( L10 = (4-hydroxy- N -methylpicolinamidate) performs better in long-term CO 2 hydrogenation (up to a TON of 14 700 with [Ir] = 10 μM after 348 h and the final formate concentration of 0.643 M with [Ir] = 250 μM) at ambient conditions. Further, the catalytic activity for FA dehydrogenation was examined under three different conditions (pH 1.6, 2.3, and 3.5). The Cp*Ir( L12 )(H 2 O)HSO 4 complex in any of these conditions is less active compared to the picolinamidate catalysts without ortho -OH, owing to its instability. The complex without OH group, Cp*Ir( L8 )(H 2 O)HSO 4 ( L8 = N -phenyl-picolinamidate), exhibits a high TOF (up to 118 000 h -1 ) at 60 °C. Theoretical calculations were performed to examine the catalytic mechanism, and a step-by-step mechanism has been proposed for both CO 2 hydrogenation and FA dehydrogenation reactions. Density functional theory calculations of [Cp*Ir( L3 )(H 2 O)]HSO 4 ( L3 = picolinamidate) and the X-ray structure of the [Cp*Ir( L7 )(H)]·H 2 O ( L7 = N -methylpicolinamidate) complex imply a pH-dependent conformational change from N , N coordination to N , O coordination upon lowering the pH of the aqueous solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Nanovoid Incorporated IrxCu Metallic Aerogels for Oxygen Evolution Reaction Catalysis

Ir-based nanomaterials are regarded as state-of-the-art cathode electrocatalysts in proton exchange membrane water electrolyzers (PEMWEs). Engineering the morphology of Ir-based three-dimensional architectures as electrocatalysts toward oxygen evolution reaction (OER) has been rarely studied. Here, we report the gelation of IrxCu metallic hydrogels self-assembled with ultrafine and nanovoid incorporated building blocks for enhancing the electrocatalytic performance toward OER. The composition-optimized Ir3Cu metallic aerogels exhibited improved catalytic activity and durability toward OER. The mesosized voids generated through the in situ galvanic replacement reaction and the macrosized porous systems make a great contribution to the increased number of active sites. First-principle calculations revealed the intrinsic optimized binding energy of Ir by alloying with Cu. The best catalytic performance necessities a balance of the adsorption and desorption energy. The well-defined morphology and enhanced OER electrochemical performances of nanovoid incorporated IrxCu metallic aerogels hold great promise in further applications in PEMWEs.

Shi, Qiurong↗

DOE OSTI2015

Temperature dependent behavior of thermal conductivity of sub-5 nm Ir film: Defect-electron scattering quantified by residual thermal resistivity

By studying the temperature-dependent behavior (300 K down to 43 K) of electron thermal conductivity (κ) in a 3.2 nm-thin Ir film, we quantify the extremely confined defect-electron scatterings and isolate the intrinsic phonon-electron scattering that is shared by the bulk Ir. At low temperatures below 50 K, κ of the film has almost two orders of magnitude reduction from that of bulk Ir. The film has ∂κ/∂T > 0, while the bulk Ir has ∂κ/∂T < 0. We introduce a unified thermal resistivity (Θ = T/κ) to interpret these completely different κ ∼ T relations. It is found that the film and the bulk Ir share a very similar Θ ∼ T trend, while they have a different residual part (Θ{sub 0}) at 0 K limit: Θ{sub 0} ∼ 0 for the bulk Ir, and Θ{sub 0} = 5.5 m·K{sup 2}/W for the film. The Ir film and the bulk Ir have very close ∂Θ/∂T (75–290 K): 6.33 × 10{sup −3} m K/W for the film and 7.62 × 10{sup −3} m K/W for the bulk Ir. This strongly confirms the similar phonon-electron scattering in them. Therefore, the residual thermal resistivity provides an unprecedented way to quantitatively evaluating defect-electron scattering (Θ{sub 0}) in heat conduction. Moreover, the interfacial thermal conductance across the grain boundaries is found larger than that of Al/Cu interface, and its value is proportional to temperature, largely due to the electron's specific heat. A unified interfacial thermal conductance is also defined and firmly proves this relation. Additionally, the electron reflection coefficient is found to be large (88%) and almost temperature independent.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS2010

Infrared Camera System for Visualization of IR-Absorbing Gas Leaks

Leak detection and location remain a common problem in NASA and industry, where gas leaks can create hazardous conditions if not quickly detected and corrected. In order to help rectify this problem, this design equips an infrared (IR) camera with the means to make gas leaks of IR-absorbing gases more visible for leak detection and location. By comparing the output of two IR cameras (or two pictures from the same camera under essentially identical conditions and very closely spaced in time) on a pixel-by-pixel basis, one can cancel out all but the desired variations that correspond to the IR absorption of the gas of interest. This can be simply done by absorbing the IR lines that correspond to the gas of interest from the radiation received by one of the cameras by the intervention of a filter that removes the particular wavelength of interest from the "reference" picture. This can be done most sensitively with a gas filter (filled with the gas of interest) placed in front of the IR detector array, or (less sensitively) by use of a suitable line filter in the same location. This arrangement would then be balanced against the unfiltered "measurement" picture, which will have variations from IR absorption from the gas of interest. By suitable processing of the signals from each pixel in the two IR pictures, the user can display only the differences in the signals. Either a difference or a ratio output of the two signals is feasible. From a gas concentration viewpoint, the ratio could be processed to show the column depth of the gas leak. If a variation in the background IR light intensity is present in the field of view, then large changes in the difference signal will occur for the same gas column concentration between the background and the camera. By ratioing the outputs, the same signal ratio is obtained for both high- and low-background signals, even though the low-signal areas may have greater noise content due to their smaller signal strength. Thus, one embodiment would use a ratioed output signal to better represent the gas column concentration. An alternative approach uses a simpler multiplication of the filtered signal to make the filtered signal equal to the unfiltered signal at most locations, followed by a subtraction to remove all but the wavelength-specific absorption in the unfiltered sample. This signal processing can also reveal the net difference signal representing the leaking gas absorption, and allow rapid leak location, but signal intensity would not relate solely to gas absorption, as raw signal intensity would also affect the displayed signal. A second design choice is whether to use one camera with two images closely spaced in time, or two cameras with essentially the same view and time. The figure shows the two-camera version. This choice involves many tradeoffs that are not apparent until some detailed testing is done. In short, the tradeoffs involve the temporal changes in the field picture versus the pixel sensitivity curves and frame alignment differences with two cameras, and which system would lead to the smaller variations from the uncontrolled variables.

Youngquist, Robert↗

NASA NTRS2022

Combined UV and IR Ozone Profile Retrieval from TROPOMI and CrIS Measurements

Vertical ozone profiles from combined spectral measurements in the ultraviolet and infrared spectral range were retrieved by using data from the TROPOspheric Monitoring Instrument on the Sentinel-5 Precursor (TROPOMI/S5P) and the Cross-track Infrared Sounder on the Suomi National Polar-orbiting Partnership (CrIS/Suomi-NPP), which are flying in loose formation 3 min apart in the same orbit. A previous study of ozone profiles retrieved exclusively from TROPOMI UV spectra showed that the vertical resolution in the troposphere is clearly limited (Mettig et al., 2021). The vertical resolution and the vertical extent of the ozone profiles is improved by combining both wavelength ranges compared to retrievals limited to UV or IR spectral data only. The combined retrieval particularly improves the accuracy of the retrieved tropospheric ozone and to a lesser degree stratospheric ozone up to 30 km. An increase in the degrees of freedom (DOF) by 1 DOF was found in the UV + IR retrieval compared to the UV-only retrieval. Compared to previous publications, which investigated combinations of UV and IR observations from the Ozone Monitoring Instrument and Tropospheric Emission Spectrometer (OMI and TES) and Global Ozone Monitoring Experiment version 2 and Infrared Atmospheric Sounding Interferometer (GOME-2 and IASI) pairs, the degree of freedom is lower, which is attributed to the reduced spectral resolution of CrIS compared to TES or IASI. Tropospheric lidar and ozonesondes were used to validate the ozone profiles and tropospheric ozone content (TOC). In their comparison with tropospheric lidars, both ozone profiles and TOCs show smaller biases for the retrieved data from the combined UV + IR observation than from the UV observations alone. For the ozone profiles below 10 km, the mean differences are around ±10 % and the mean TOC varies around ±3 DU. We show that TOCs from the combined retrieval agree better with ozonesonde results at northern latitudes than the UV-only and IR-only retrievals and also have lower scatter. In the tropics, the IR-only retrieval shows the best agrement with TOCs derived from ozonesondes. While in general the TOCs show good agreement with ozonesonde data, the profiles have a positive bias of around 30 % between 10 and 15 km. The reason is probably a positive stratospheric bias from the IR retrieval. The comparison of the UV + IR and UV ozone profiles up to 30 km with the Microwave Limb Sounder (MLS) demonstrates the improvement of the UV + IR profile in the stratosphere above 18 km. In comparison to the UV-only approach the retrieval shows improvements of up to 10 % depending on latitude but can also show worse results in some regions and latitudes.

Ozone↗

DOE OSTI2014

Highly Active and Stable MgAl2O4 Supported Rh and Ir Catalysts for Methane Steam Reforming: A Combined Experimental and Theoretical Study

In this work we present a combined experimental and theoretical investigation of stable MgAl2O4 spinel-supported Rh and Ir catalysts for the steam methane reforming (SMR) reaction. Firstly, catalytic performance for a series of noble metal catalysts supported on MgAl2O4 spinel was evaluated for SMR at 600-850°C. Turnover rate at 850°C follows the order: Pd > Pt > Ir > Rh > Ru > Ni. However, Rh and Ir were found to have the best combination of activity and stability for methane steam reforming in the presence of simulated biomass-derived syngas. It was found that highly dispersed ~2 nm Rh and ~1 nm Ir clusters were formed on the MgAl2O4 spinel support. Scanning Transition Electron Microscopy (STEM) images show that excellent dispersion was maintained even under challenging high temperature conditions (e.g. at 850°C in the presence of steam) while Ir and Rh catalysts supported on Al2O3 were observed to sinter at increased rates under the same conditions. These observations were further confirmed by ab initio molecular dynamics (AIMD) simulations which find that ~1 nm Rh and Ir particles (50-atom cluster) bind strongly to the MgAl2O4 surfaces via a redox process leading to a strong metal-support interaction, thus helping anchor the metal clusters and reduce the tendency to sinter. Density functional theory (DFT) calculations suggest that these supported smaller Rh and Ir particles have a lower work function than larger more bulk-like ones, which enables them to activate both water and methane more effectively than larger particles, yet have a minimal influence on the relative stability of coke precursors. In addition, theoretical mechanistic studies were used to probe the relationship between structure and reactivity. Consistent with the experimental observations, our theoretical modeling results also suggest that the small spinel-supported Ir particle catalyst is more active than the counterpart of Rh catalyst for SMR. This work was financially supported by the United States Department of Energy (DOE)’s Bioenergy Technologies Office (BETO) and performed at the Pacific Northwest National Laboratory (PNNL). PNNL is a multi-program national laboratory operated for DOE by Battelle Memorial Institute. Computing time was granted by a user proposal at the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) located at PNNL. Part of the computational time was provided by the National Energy Research Scientific Computing Center (NERSC).

ab initio molecular dynamics↗

DOE OSTI2013

Magnetic behavior of the Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7} pyrochlore solid solution

The temperature dependence of magnetic susceptibility of the Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7} system was studied from 2 to 300 K. According to these measurements, the solid solution (0≤y≤0.9) does not show any magnetic transition; however, a noticeable deviation from the Curie–Weiss law occurs and the magnetic behavior of this system can be ascribed to short-range magnetic order that is also present in several geometrically frustrated systems. The Pauli magnetic susceptibility decreases as the Sr content increases, this can be associated with a shift towards Ir{sup 5+} in samples; also the Ir effective magnetic moment decreases. The estimated Wilson-ratio indicates the presence of strong electron–electron correlations. - Graphical abstract: Temperature dependence of the magnetic susceptibility of Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7}. The samples of this system showed no magnetic transition down to 2 K. Analyzing magnetic data (symbols for experimental data, continuous line for the Curie–Weiss (CW) equation and black dots for a modified CW equation), it is found that this system departures from a CW-like equation and the magnetic parameters C and θ notably deviate from the expected values for Ir. Better fittings with a modified CW equation are shown in the A and B insets. Highlights: ► The magnetic susceptibility of the Bi{sub 2−x}Sr{sub x}Ir{sub 2}O{sub 7} system is discussed. ► No magnetic transition is observed. ► Magnetic measurements on the Bi{sub 2−y}Sr{sub y}Ir{sub 2}O{sub 7} indicate the existence of Ir{sup 5+}. ► The magnetic susceptibility does not follow a Curie–Weiss law. ► A modified Curie–Weiss equation describes correctly the magnetic susceptibility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

The Chemical and Electronic Properties of Stability-Enhanced, Mixed Ir-TiO x Oxygen Evolution Reaction Catalysts

Iridium has emerged as the leading catalyst material for the anodic oxygen evolution reaction (OER) in acidic media. Often, iridium is mixed with more stable materials such as titanium. For these materials, the electronic structure of titanium plays a crucial role since with varying degrees of oxidation titanium transforms to semiconducting or even insulating phases. Yet, the electronic properties of mixed Ir-TiO x catalysts have never been systematically studied. In this study, we correlate the catalytic performance of mixed Ir-TiO x -based OER catalysts with the electronic structure of the surface layers. For this, a thin film material library with a 20-70 at. % Ir (Ir/[Ir + Ti]) compositional gradient was prepared. We used inductively coupled plasma mass spectrometry to test the OER activity and stability of the set of mixed Ir-TiO x catalyst candidate materials. Complementary, Ti L 2,3 - and O K-edge X-ray absorption spectroscopy and depth-dependent X-ray photoelectron spectroscopy measurements were performed to correlate the catalytic performance with the composition and electronic property profiles of these mixed Ir-TiO x OER anode catalysts. The spectroscopic analysis reveals that titanium is present as an intermixed matrix of semiconductive but stable TiO 2 , conductive but less stable titanium-suboxides (TiO x ), and highly conductive but highly unstable metallic Ti(0). The extent of the titanium oxidation strongly depends on the titanium content, with a lower degree of oxidation observed for lower titanium (and thus higher iridium) contents. For an iridium loading of 70 at. %, the respective mixed Ir-TiO x catalyst showed a similar OER activity to that of the pure metallic iridium (1.74 vs 1.59 VRHE, respectively) but with a 71% lower iridium dissolution rate relative to the pure metallic iridium. This demonstrates the stabilization effect of titanium addition while maintaining high OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Searching for a route to synthesize in situ epitaxial Pr 2 Ir 2 O 7 thin films with thermodynamic methods

In situ growth of pyrochlore iridate thin films has been a long-standing challenge due to the low reactivity of Ir at low temperatures and the vaporization of volatile gas species such as IrO 3 (g) and IrO 2 (g) at high temperatures and high P O2 . To address this challenge, we combine thermodynamic analysis of the Pr-Ir-O 2 system with experimental results from the conventional physical vapor deposition (PVD) technique of co-sputtering. Our results indicate that only high growth temperatures yield films with crystallinity sufficient for utilizing and tailoring the desired topological electronic properties and the in situ synthesis of Pr 2 Ir 2 O 7 thin films is fettered by the inability to grow with P O2 on the order of 10 Torr at high temperatures, a limitation inherent to the PVD process. Thus, we suggest techniques capable of supplying high partial pressure of key species during deposition, in particular chemical vapor deposition (CVD), as a route to synthesis of Pr 2 Ir 2 O 7 .

Chemistry↗