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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2019

Utilization of Airborne Observations to Assess Model Parametrizations of Critical RH Profiles in the Arctic Ocean

Observational paucity is a reality in the Arctic Ocean. This is especially true for near-surface variables such as temperature, moisture, heat fluxes and BL clouds. As a result, modeling has become one of the major avenues for understanding current and future Arctic trends. Reanalyses are frequently used to force global ocean circulation and sea-ice models. But in northern high latitudes, model integrations and reanalyses are known to have large uncertainties in temperature and humidity profiles, and in boundary layer cloudiness. These are common sources of error in the surface radiative budget terms.An important way to diagnose these biases spatially and temporally is by using satellite remote sensing data. However, remotely-sensed observations also have large uncertainties, especially in near-surface temperature and relative humidity profiles.In situ observational studies are important in bridging our knowledge gap in regions such as the Arctic Ocean. Here, we utilize airborne and ship observations from the ARISE, ACME-IV, and ASCOS campaigns to construct critical relative humidity (RH) profiles over the Beaufort Sea. Such profiles are used as parameterization inputs in the NASA GOES global model to derive the total water condensate in a model grid-box, which determines the cloud fraction. Currently, the critical RH profiles are derived by global AIRS data, relaying mostly on mid-latitude regions, which are not necessarily relevant to the Arctic.We derive campaign-wide mean, standard deviation, and critical RH values, for grid size of 50x50 km and altitude bins between 50 to 400 m, covering both open-ocean and sea-ice covered regions. We compare profiles over open ocean and sea-ice, and look at correlations between the observed critical RH values and water condensate (by cloud number concentration) from observations versus the modeled ones. We then input our calculated values of minimal critical RH values into a set of GEOS single column model (SCM) simulations over the ARISE and ASCOS regions and compare the differences between the predicted values of cloud liquid water path (LWP), ice water path (IWP) and surface fluxes with the observed ones under the range of input parameterizations. Finally, we discuss the implications on surface radiative budget predictions in this region.

Segal-Rozenhaimer, Michal↗
DOE OSTI2021

Neural network potential for Zr–Rh system by machine learning

Zr–Rh metallic glass has enabled its many applications in vehicle parts, sports equipment and so on due to its outstanding performance in mechanical property, but the knowledge of the microstructure determining the superb mechanical property remains yet insufficient. Here, we develop a deep neural network potential of Zr–Rh system by using machine learning, which breaks the dilemma between the accuracy and efficiency in molecular dynamics simulations, and greatly improves the simulation scale in both space and time. Here, the results show that the structural features obtained from the neural network method are in good agreement with the cases in ab initio molecular dynamics simulations. Furthermore, we build a large model of 5400 atoms to explore the influences of simulated size and cooling rate on the melt-quenching process of Zr 77 Rh 23 . Our study lays a foundation for exploring the complex structures in amorphous Zr 77 Rh 23 , which is of great significance for the design and practical application.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

NO Reduction with CO on Low‐loaded Platinum‐group Metals (Rh, Ru, Pd, Pt, and Ir) Atomically Dispersed on Ceria

Abstract Low‐loaded platinum‐group single‐atom catalysts on CeO 2 (M 1 /CeO 2 ) were synthesized via high‐temperature atom trapping (AT) and tested for the NO+CO reaction under dry and wet conditions. The activity of these catalysts for NO+CO reaction follows the order Rh>Pd≈Ru>Pt>Ir. For Rh, Ru, and Pd single‐atom catalysts, the N 2 O byproduct is formed but not clearly observed in Ir and Pt cases, which may result from the higher reaction temperature (>200 °C) required for Pt and Ir catalysts. The presence of water can promote the activity of these M 1 /CeO 2 catalysts for the NO+CO reaction. Under wet conditions, significant NH 3 formation occurred during the reaction, which is due to the co‐existence of water‐gas‐shift reaction on these catalysts. Compared with Pt, Pd and Ir, the Rh and Ru single‐atom catalysts show higher selectivity to NH 3 species, resulting from the hydride species on the surface. Among all tested catalysts, Ru 1 /CeO 2 shows the highest production of ammonia and highest CO conversion due to excellent water‐gas‐shift activity, whereas Pd 1 /CeO 2 shows lowest ammonia production. Rh 1 /CeO 2 shows the best low temperature NO reduction activity among all tested catalysts.

Tian, Jinshu↗
DOE OSTI2022

Surface Fe clusters promote syngas reaction to oxygenates on Rh catalysts modified by atomic layer deposition

Converting syngas to higher oxygenates is a promising strategy for sustainably producing fuels and chemicals used every day. Rh-based catalysts promoted with metal oxides have long been of interest for oxygenate synthesis, but the role of promoters and the structure of the catalyst during reaction are often not well understood. In this work, we characterize a Rh/SiO 2 catalyst modified by Fe 2 O 3 deposited by atomic layer deposition (ALD). Here, we show that Fe 2 O 3 deposits selectively on the Rh nanoparticles and enhances both the turnover frequency and the oxygenate selectivity of the catalysts. A maximum 29% selectivity towards higher oxygenates is achieved with just 1 cycle of Fe 2 O 3 ALD, and we relate the trends in selectivity to the changing availability of surface sites that drive higher alcohol (e.g., ethanol and propanol) formation. Further, we show that the ALD promoter mitigates catalyst sintering, improving the stability of these materials. In-situ X-ray absorption spectroscopy experiments reveal that the Fe 2 O 3 undergoes reduction during the catalyst pretreatment and forms Fe clusters on the surface of the Rh that migrate but remain stable under syngas reaction conditions. We find that modification of the Rh with these surface Fe species is key to the enhanced alcohol production observed in these materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Complex Dirac-like Electronic Structure in Atomic Site-Ordered Rh 3 In 3.4 Ge 3.6

We report the synthesis via an indium flux method of a novel single-crystalline compound Rh 3 In 3.4 Ge 3.6 that belongs to the cubic Ir 3 Ge 7 structure type. In Rh 3 In 3.4 Ge 3.6 , the In and Ge atoms preferentially occupy, respectively, the 12d and 16f sites of the Im3¯m space group, thus creating a colored variant of the Ir 3 Ge 7 structure. Like the other compounds of the Ir 3 Ge 7 family, Rh 3 In 3.4 Ge 3.6 shows potential as a thermoelectric, displaying a relatively large power factor, PF ~ 2 mW/cm K 2 , at a temperature T ~ 225 K, albeit showing a modest figure of merit, ZT = 8 x 10 -4 , because of the lack of a finite band gap. These figures might improve through a use of chemical substitution strategies to achieve band gap opening. Remarkably, electronic band structure calculations reveal that this compound displays a complex Dirac-like electronic structure relatively close to the Fermi level. The electronic structure is composed of several Dirac type-I and type-II nodes, and even Dirac type-III nodes that result from the touching between a flat band and a linearly dispersing band. Here, this rich Dirac-like electronic dispersion suggests the possibility to observe experimentally Dirac type-III nodes and study their role in the physical properties of Rh 3 In 3.4 Ge 3.6 and related Ir 3 Ge 7 -type materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Single-Atom Doping at the Molecule–Metal Interface: How Rh Affects Surface Explosion Kinetics

Controlling chemical reactions at interfaces is central to many fields, including atmospheric, environmental, and biological chemistry as well as catalysis and corrosion. We performed a fundamental study of how catalytically active Rh atoms placed at and above a molecule-metal interface influence the surface reaction kinetics of tartaric acid (TA) decomposition. Specifically, TA decomposition on Cu(100) exhibits autocatalytic decomposition kinetics involving a slow initiation step followed by fast decomposition of the molecular layer. These so-called “surface explosions” are extremely sensitive to initial conditions, making it fundamentally interesting to study how the placement of reactive atoms affects the reaction rate. Temperature-programmed reaction (TPR) experiments reveal that Rh atoms embedded in the Cu(100) surface beneath TA (TA/Rh/Cu) or atop the TA layer (Rh/TA/Cu) reduce the decomposition temperature and modify the reaction rate constants. Isothermal TPR analysis reveals that Rh enhances both the initiation rate constant, k i , and the explosion rate constant, k e , facilitating explosive decomposition at lower temperatures. This result provides evidence that both the initiation and explosion steps occur at the metal-molecule interface and are accelerated by the presence of Rh at this interface. This study illustrates how small amounts of reactive elements may be used to control nonlinear kinetic processes at interfaces.

desorption↗
DOE OSTI2025

Metal–Metal Bonding Influences Hydride Reactivity in [Sn–Rh] 3+ and [Sn–Ni] 2+ Bimetallics

Heavier group 14 metal hydrides serve as key intermediates in catalytic transformations, such as hydroboration. Regenerating such intermediates via a clean hydride source like dihydrogen could provide catalytic processes with a more economical alternative to, e.g., silanes and hydridoborane reagents. Herein, we report our efforts toward this goal using a [Sn–Rh] 3+ bimetallic system with the formal Rh I center acting as a potential dihydrogen activator. Targeting the introduction of a hydride ligand to the bimetallic core, our reactivity studies have revealed a preference for the hydride ligand to be bound to the Rh center, instead of the Sn center. Finally, examination of the electronic structures of these complexes via theoretical and experimental methods has revealed the electron acceptor nature of the Rh center within the bimetallic core and offers an explanation for the localization of the hydride between metal centers.

anions↗
DOE OSTI2020

Enhancing superconductivity of Y 5 Rh 6 Sn 18 by atomic disorder

Here, we investigate the effect of enhancement of superconducting transition temperature $T_c$ by nonmagnetic atom disorder in the filled skutterudite-related tetragonal Y 5 Rh 6 Sn 18 compound doped with Ca. We documented experimentally that Y 5 Rh 6 Sn 18 and its Ca-doped alloys are electronically inhomogeneous at the nanoscale, when Ca content is smaller than ~1.5 in the Y 5– x Ca x Rh 6 Sn 18 system, while for $\textit{x}$ ≥ 1.5 much stronger chemical phase inhomogeneity is observed with an about 20% volume fraction of the second 3:4:13 cubic phase, which we interpret as a fluctuation of stoichiometry within the bulk sample. Then the enhancement of $T_c$ vs $\textit{x}$ could be modeled by a mechanism proposed in recent theoretical reports for increasing the mean-field transition temperature $T_c$ in the presence of nonmagnetic disorder. The increase in disorder with doping increases the sample inhomogeneity and causes a systematic increase in $T_c$, while for two-phase $\textit{x}$ ≥ 1.5 samples the critical temperature $T^{\star}_c ≈ 2 × T_c$ rapidly increases. Based on band structure calculations performed under pressure, we demonstrate how the change in density of states would affect $T_c$ of Y 5 Rh 6 Sn 18 . We obtained the Grüneisen parameter $γ_G$ larger for the inhomogeneous phase with respect to $γ_G$ of the bulk $T_c$ phase and attribute the enhancement of $T_c$ to larger stiffening of the high-temperature $T^{\star}_c$ phase.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Possible unconventional pairing in ( Ca , Sr ) 3 ( Ir , Rh ) 4 Sn 13 superconductors revealed by controlling disorder

Here we study the evolution of temperature-dependent resistivity with added pointlike disorder induced by 2.5 MeV electron irradiation in stoichiometric compositions of the “3-4-13” stannides, (Ca,Sr) 3 (Ir,Rh) 4 Sn 13 . Three of these cubic compounds exhibit a proposed microscopic coexistence of charge density wave (CDW) order and superconductivity (SC), while Ca 3 Rh 4 Sn 13 does not develop CDW order. As expected, the CDW transition temperature T CDW is universally suppressed by irradiation in all three compositions. The superconducting transition temperature, T c , behaves in a more complex manner. In Sr 3 Rh 4 Sn 13 , it increases initially in a way consistent with a direct competition of CDW and SC, but quickly saturates at higher irradiation doses. In the other three compounds, T c is monotonically suppressed by irradiation. The strongest suppression is found in Ca 3 Rh 4 Sn 13 , which does not have CDW order. We further examine this composition by measuring the London penetration depth λ(T), from which we derive the superfluid density. The result unambiguously points to a weak-coupling, full single gap, isotropic superconducting state. Therefore we must explain two seemingly incompatible experimental observations: a single isotropic superconducting gap and a significant suppression of T c by nonmagnetic disorder. We conduct a quantitative theoretical analysis based on a generalized Anderson theorem which points to an unconventional multiband s +– -pairing state where the sign of the order parameter is different on one (or a small subset) of the smaller Fermi surface sheets but remains isotropic and overall fully gapped.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , a New Mineral Species from the Sisim Placer Zone, Eastern Sayans, Russia, and the Torryweiserite–Ferrotorryweiserite Series

Ferrotorryweiserite, Rh 5 Fe 10 S 16 , occurs as small grains (≤20 µm) among droplet-like inclusions (up to 50 μm in diameter) of platinum-group minerals (PGM), in association with oberthürite or Rh-bearing pentlandite, laurite, and a Pt-Pd-Fe alloy (likely isoferroplatinum and Fe-Pd-enriched platinum), hosted by placer grains of Os-Ir alloy (≤0.5 mm) in the River Ko deposit. The latter is a part of the Sisim placer zone, which is likely derived from ultramafic units of the Lysanskiy layered complex, southern Krasnoyarskiy kray, Russia. The mineral is opaque, gray to brownish gray in reflected light, very weakly bireflectant, not pleochroic to weakly pleochroic (grayish to light brown tints), and weakly anisotropic. The calculated density is 5.93 g·cm –3 . Mean results (and ranges) of four WDS analyses are: Ir 18.68 (15.55–21.96), Rh 18.34 (16.32–20.32), Pt 0.64 (0.19–1.14), Ru 0.03 (0.00–0.13), Os 0.07 (0.02–0.17), Fe 14.14 (13.63–14.64), Ni 13.63 (12.58–14.66), Cu 4.97 (3.42–6.41), Co 0.09 (0.07–0.11), S 29.06 (28.48–29.44), and total 99.66 wt.%. They correspond to the following formula calculated for a total of 31 atoms per formula unit: (Rh 3.16 Ir 1.72 Pt 0.06 Ru 0.01 Os 0.01 ) Σ 4.95 (Fe 4.48 Ni 4.11 Cu 1.38 Co 0.03 ) Σ10.00 S 16.05 . The results of synchrotron micro-Laue diffraction studies indicate that ferrotorryweiserite is trigonal; its probable space group is $R\bar{3}m$ (#166) based on its Ni-analog, torryweiserite. The unit-cell parameters refined from 177 reflections are a = 7.069 (2) Å, c = 34.286 (11) Å, V = 1484 (1) Å 3 , and Z = 3. The c:a ratio is 4.8502. The strongest eight peaks in the X-ray diffraction pattern derived from results of micro-Laue diffraction study [d in Å(hkil)(I)] are 2.7950 ($20\bar{2}5$) (100); 5.7143 (0006) (60); 1.7671 ($22\bar{4}0$) (44.4); 3.0486 ($20\bar{2}1$) (39.4); 5.7650 ($10\bar{1}2$) (38.6); 2.5956 ($20\bar{2}7$) (37.8); 3.0058 ($11\bar{2}6$) (36.5); and 1.5029 ($4\bar{2}\bar{2}12$) (35.3). Ferrotorryweiserite and the associated PGM crystallized from microvolumes of residual melt at late stages of crystallization of grains of Os- and Ir-dominant alloys occurred in lode zones of chromitites of the Lysanskiy layered complex. In a particular case, the residual melt is disposed peripherally around a core containing a disequilibrium association of magnesian olivine (Fo 72.9–75.6 ) and albite (Ab 81.6–86.4 ), with the development of skeletal crystals of titaniferous augite: Wo 40.8–43.2 En 26.5–29.3 Fs 20.3–22.6 Aeg 6.9–9.5 (2.82–3.12 wt.% TiO 2 ). Ferrotorryweiserite represents the Fe-dominant analog of torryweiserite. We also report occurrences of ferrotorryweiserite in the Marathon deposit, Coldwell Complex, Ontario, Canada, and infer the existence of the torryweiserite–ferrotorryweiserite solid solution in other deposits and complexes.

58 GEOSCIENCES↗
DOE OSTI2020

Materials Data on Rh(N2O3)3 by Materials Project

Rh(N2O3)3 crystallizes in the trigonal P3 space group. The structure is zero-dimensional and consists of one nsc241243 molecule. Rh4+ is bonded in a 6-coordinate geometry to three equivalent N+2.33+ and three equivalent O2- atoms. All Rh–N bond lengths are 1.82 Å. All Rh–O bond lengths are 2.21 Å. There are two inequivalent N+2.33+ sites. In the first N+2.33+ site, N+2.33+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of N–O bond distances ranging from 1.23–1.34 Å. In the second N+2.33+ site, N+2.33+ is bonded in a distorted single-bond geometry to one Rh4+ atom. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Rh4+ and one N+2.33+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one N+2.33+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one N+2.33+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Oxygen Adsorption, Subsurface Oxygen Layer Formation and Reaction with Hydrogen on Surfaces of a Pt–Rh Alloy Nanocrystal

The oxygen adsorption and its catalytic reaction with hydrogen on Pt–Rh single crystals were studied at the nanoscale by Field Emission Microscopy (FEM) and Field Ion Microscopy (FIM) techniques at 700 K. Both FEM and FIM use samples prepared as sharp tips, apexes of which mimic a single nanoparticle of catalyst considering their similar size and morphology. Oxygen adsorption on Pt-17.4 at.%Rh samples leads to the formation of subsurface oxygen, which is manifested in the field emission (FE) patterns: for O2 exposure of ~3 Langmuir (L), {113} planes appear bright in the emission pattern, while for higher oxygen doses, i.e. 84 L, the bright regions correspond to the high index planes between the {012} and {011} planes. Formation of subsurface oxygen is probably accompanied by a surface reconstruction of the nanocrystal. The subsurface oxygen can be effectively reacted off by subsequent exposure of the sample to hydrogen gas at 700 K. The hydrogenation reaction was observed as a sudden, eruptive change of the brightness seen on the FE pattern. This reaction resulted in the recovery of the initial field emission pattern characteristic of a clean tip, with {012} facets being the most visible. It was shown that the oxygen accumulation-reduction process is completely reversible. The obtained results indicate that the presence of subsurface species must be considered in the description of reactive processes on Pt–Rh catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

A comparative study on cubic and tetragonal Ce-ZrO 2 supported Rh catalysts for N 2 O decomposition

Zirconium oxide (ZrO 2 ) exhibits strong synergy with cerium oxide (CeO 2 ), acting as a structural and electronic promoter during catalytic redox reactions. As a result, Ce-ZrO 2 composite oxides are widely used as supports in various catalytic systems. In our previous work, we demonstrated that the incorporation of Zr 4+ into the CeO 2 lattice significantly enhanced Rh dispersion, improved redox ability, and stabilized surface Rh species, which collectively boosted the de-N 2 O activity of Rh/Ce-ZrO 2 catalysts. Building on these findings, the present study emphasizes that the crystallographic phase of Ce-ZrO 2 , governed by the Ce/Zr ratio, plays a decisive role in tuning the physicochemical environment of Rh active sites and thereby optimizing catalytic performance. In conclusion, tailoring the Ce/Zr ratio to favor the cubic fluorite structure emerges as a promising strategy for the rational design of highly active and stable catalysts for N 2 O decomposition and potentially other redox-sensitive environmental applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface: A first principles study

Microkinetic models based on first principles calculations have been used to study the vapor and liquid phase hydrodeoxygenation of propionic acid on a Rh(111) surface. Calculations suggest that both decarboxylation and decarbonylation do not occur at an appreciable rate under all reaction environments. Propanol and propionaldehyde are the main products on this surface and they are produced at similar rates in both vapor and liquid phase environments. While a condensed phase can shift the reaction rate, the dominant pathways and selectivity towards the various products are hardly affected. At 473 K, the turnover frequency is increased by about a factor of 1.5 in liquid water relative to the gas phase. In liquid 1,4-dioxane, the turnover frequency is also slightly increased relative to the gas phase. Here, given the uncertainty in Rh cavity radius in the liquid phase calculations, computations with different cavity radii have been performed. With larger Rh cavity radius, the promotional effect of the solvents on the turnover frequency becomes more significant, while practically no changes are observed for a smaller cavity radius.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

DFT Mechanism Studies: Biomimetic 1,4-NADH Chemoselective, Co-factor Regeneration with [Cp*Rh(bpy)H] + , in Tandem with the Biocatalysis Pathways of a Core Model of the (HLADH)-Zn(II) Mediated Enzyme, in the Enantioselective Reduction of Achiral Ketones to Chiral S-Alcohols

In this study, Quantum Chemical (QC) calculations, utilizing Density Functional Theory (DFT), were performed to investigate the mechanistic aspects of the chemoselective catalyzed reaction of [Cp*Rh(bpy)H] + with the biomimetic NAD + analogues, N-benzylnicotinamide triflate, 1, and β-nicotinamide ribose-5'-methyl phosphate, 2, in the conversion to their 1,4-NADH analogues, 1,4-dihydro-N-benzylnicotinamide, 4, and β-1,4-dihydronicotinamide-5'-ribose methyl phosphate, 5. This reaction was in tandem with the 1,4-NADH dependent HLADH-Zn(II)- catalyzed reduction of achiral ketones to chiral S-alcohols. The [Cp*Rh(bpy)H] + complex, and not its equilibrium tautomer, [η 4 -Cp*HRh(bpy)] + , was found to control the hydride transfer during the biomimetic NAD + /1,4-NADH conversion, through the non-covalent interactions of the biomimetic co-factors with [Cp*Rh(bpy)H] + . The thermodynamics and kinetics for the chiral reduction of the Zn(II) bound ketones, 2-pentanone and 4-phenyl-2-butanone, with co-factor, 4, catalyzed by Zn(SCH 3 ) 2 (Imidazole), a core model of the Zn(II)-based catalytic center of HLADH, was also investigated by the evaluation of two possible reaction pathways: (1) formation of a ZnH from the C4-H hydride transfer of co-factor, 4, followed by reaction of the postulated ZnH with the bound 2-pentanone or 4-phenyl-2-butanone substrate, and (2), the direct C4-H transfer to the bound achiral ketone substrates, to provide the dominant chiral alcohols, S-2-pentanol or S-4-phenyl-2-butanol. The latter pathway was found most viable, and DFT calculations also revealed an essential η 2 -coordination of the 5,6 double bond of co-factor, 4, to the HLADH-Zn(II) metal ion center, upon imidazole decomplexation, providing an asymmetric differentiation of S-η 2 -5,6-1,4-NADH-Zn(II) binding. A proposed new paradigm for the Zn(II)'s non-innocent role in the HLADH-Zn(II) biocatalysis reduction mechanism, for enantioselective hydride transfer to a Zn(II) bound ketone, providing S-alcohols.

1,4 NADH co-factors↗
DOE OSTI2025

Ethyl transfer reactions of NaBEt 4 with Cp*Rh(PMe 3 )PhBr and elimination reactions

The reaction of NaBEt 4 with Cp*Rh(PMe 3 )PhBr produces Cp*Rh(PMe 3 )PhEt by ethyl transfer. Single crystal X-ray analysis shows a typical piano-stool geometry. This compound reacts photochemically (λ > 320 nm) to give Cp*Rh(PMe 3 )PhH as the major product, plus ethylene. A secondary product was assigned as the square planar complex RhPh(PMe 3 )(η 4 -C 5 Me 5 Et) on the basis of NMR spectroscopy. Finally, the molecule decomposes over several days at ambient temperature, releasing C 5 Me 5 Et.

02 PETROLEUM↗
DOE OSTI2024

Formation of (Rh–Fe)–FeO x Complex Sites Enables Methanol Synthesis from CO 2

Here, we addressed the challenges of designing catalysts for selective CO 2 hydrogenation by incorporating oxide Fe species onto Rh nanoparticles. Nanoscopic FeO x domains created a “reverse catalyst” structure (i.e., a metal oxide supported on a metal) that increased the density of interfacial sites compared to traditional supported catalysts. The contact between the metal nanoparticle and the oxide overlayer induced the formation of a surface Rh-Fe alloy that stabilize methoxy groups while suppressing hydrogenolysis to methane. Sites at FeO x -metal interfaces interact with CO 2 sevenfold stronger than sites on metal surfaces, show larger energy barriers to cleave the C-O bonds, and offer a barrierless pathway for hydrogenation of methoxy species to methanol. Consequently, the multifunctional sites over FeO x /Rh-Fe catalysts highlight and meet the requirements of a selective methanol catalyst: strong interaction with CO 2 to ensure high density of transition states; metal sites to activate and make hydrogen available to surface intermediates; and high energy barriers for C-O bond cleavage to form carbides. These synthesis and catalytic chemistries, demonstrated for Rh-Fe-FeO x interfaces, enable us to overcome the limitations to the design of methanol production catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

In Crystallo Snapshots of Rh 2 -Catalyzed C–H Amination

While X-ray crystallography routinely provides structural characterization of kinetically stable pre-catalysts and intermediates, elucidation of the structures of transient reactive intermediates, which are intimately engaged in bond-breaking and -making during catalysis, is generally not possible. Here, we demonstrate in crystallo synthesis of Rh 2 nitrenoids that participate in catalytic C-H amination, and characterize these transient intermediates as triplet adducts of Rh 2 . Further, we observe the impact of coordinating substrate, which is present in excess during catalysis, on the structure of transient Rh 2 nitrenoids. By providing structural characterization of authentic C-H functionali-zation intermediates, and not kinetically stabilized model complexes, these experiments provide the opportunity to define critical structure-activity relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗