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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.

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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Hydrothermal synthesis and thermal change in IR reflectance of Al/W co-doped VO2 powder

Highlights: • Al/W-doped VO{sub 2} powders were synthesized by a hydrothermally method. • The Al/W-doped VO{sub 2} underwent a phase transition at around room temperature. • The Al/W-doped VO{sub 2} had the larger IR reflectance compared with W-VO{sub 2}(M). - Abstract: Al/W co-doped VO{sub 2} with a monoclinic structure, space group P2{sub 1}/c, was synthesized (hereafter, Al/W-doped VO{sub 2}(M1)) and its thermochromic property was investigated. First, to prepare the precursor for Al/W-doped VO{sub 2}(M1), V{sub 2}O{sub 5}, (NH{sub 4}){sub 10}W{sub 12}O{sub 41}·5H{sub 2}O, and AlCl{sub 3}·H{sub 2}O were dispersed in a citric acid solution and then hydrothermally treated in an autoclave. Then, the Al/W-doped VO{sub 2}(M1) powders were synthesized by heating the obtained precursor at various temperatures under an Ar gas flow. The Al/W-doped VO{sub 2}(M1) has a monoclinic structure with space group P2{sub 1}/c, similar to undoped VO{sub 2}(M1) and W-doped VO{sub 2}(M1). The Al/W-doped VO{sub 2}(M1) indicated that the monoclinic to tetragonal transition temperature was lowered to approximately room temperature by the Al and W doping. The Al/W-doped VO{sub 2}(M1) had the lower optical band gap and showed a larger IR reflectance in the 800–2000 nm range, compared with W-doped VO{sub 2}(M1) and pure VO{sub 2}(M1).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Oxygen deficiency induced nickel based oxides for UV & IR sensitive photo-conductive devices

Ni(NO{sub 3}){sub 3}.6H{sub 2}O has been thermally decomposed to synthesize NiO{sub x} (0 3-δ synthesis. These metal oxides have been characterized by XRD, SEM, TEM, XPS and UV–vis spectroscopy for the determination of their crystal structures, structural morphologies, oxidation states and optical band gaps. The devices, made of nanocrystalline-composites or nanocomposites, have been fabricated on gold coated soda lime glasses, where the device based on NiO{sub x} has been found applicable for UV photo-conducting and LaNiO{sub 3-δ} has been recognized as a potential IR photo-conducting sensors. Their respective current amplifications have been recorded 8 and 2.2 times more than the dark current at 2 V of DC bias. The UV sensor has been explained by direct band gap semiconducting nature of NiO{sub x} and IR sensitivity of LaNiO{sub 3-δ} was explained in terms oxygen deficiency induced band gap opening.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2016

Tuning electrocatalytic activity of Pt monolayer shell by bimetallic Ir-M (M=Fe, Co, Ni or Cu) cores for the oxygen reduction reaction

Here, platinum monolayer electrocatalyst are known to exhibit excellent oxygen reduction reaction (ORR) activity depending on the type of substrate used. Here we demonstrate a relationship between the ORR electrocatalytic activity and the surface electronic structure of Pt monolayer shell induced by various IrM bimetallic cores (M=Fe, Co, Ni or Cu). The relationship is rationalized by comparing density functional theory calculations and experimental results. For an efficient Pt monolayer electrocatalyst, the core should induce sufficient contraction to the Pt shell leading to a downshift of the d-band center with respect to the Fermi level. Depending on the structure of the IrM, relative to that of pure Ir, this interaction not only alters the electronic and geometric structure but also induces segregation effects. Combined these effects significantly enhance the ORR activities of the Pt monolayer shell on bimetallic Ir cores electrocatalysts.

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

Quantum fisher information reveals UV-IR mixing in the strange metal

The density-density response in optimally doped Bi 2 Sr 2 CaCu 2 O 8+$x$ has recently been shown to exhibit conformal symmetry. Using, the experimentally inferred conformal dynamic susceptibility, we compute the resultant quantum Fisher information (QFI), a witness to multi-partite entanglement. For a Fermi liquid, we find that the QFI grows quadratically as the temperature increases, consistent then with the phase space available for scattering in the standard theory of metals. By contrast, the QFI in a strange metal increases as a power law at as the temperature decreases, but ultimately extrapolates to a constant at T=0. The constant is of the form, ω$^{2Δ}_g$, where Δ is the conformal dimension and ω g is the UV cutoff which is on the order of the pseudogap. As this constant depends on both UV and IR properties, it illustrates that multipartite entanglement in a strange metal exhibits UV-IR mixing, a benchmark feature of doped Mott insulators as exemplified by dynamical spectral weight transfer. We conclude with a discussion of the implication of our results for low-energy reductions of the Hubbard model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Joint influence of γ–irradiation and high temperature shear grinding on the IR spectra and surface–energy properties of polyethylene

The optical and surface-energy properties of polyethylene (PE) subjected to γ-irradiation and post-radiation, high temperature, shear grinding are presented. Comparison of the IR spectra of the initial and γ-irradiated PE shows that oxygen-containing groups and unsaturated bonds in the polymer macromolecules are formed and accumulate during their radiolysis in air, increasing with γ-irradiation dose. A redistribution of the products of radiation-chemical conversion on the surface of the polymer granules throughout the entire volume of the powder occurs after high-temperature shear milling to a powder as observed in the IR spectrum. Polar functional groups due to oxidation reactions are observed on the surface layer of the sample after post-radiation grinding. Furthermore, the initial polymer surface is weakly basic with an acidity parameter of -0.34. The value of the acidity parameter of the sample made of ground irradiated PE has an acidic surface with an acidity parameter of 0.65. γ irradiation of the secondary processing of PE waste with high-temperature shear grinding is a promising approach to obtain a secondary PE powder with specified parameters and different degrees of functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy

Aqueous proton transport involves the ultrafast interconversion of hydrated proton species that are closely linked to the hydrogen bond dynamics of water, which has been a long-standing challenge to experiments. In this study, we use ultrafast IR spectroscopy to investigate the distinct vibrational transition centered at 1750 cm –1 in strong acid solutions, which arises from bending vibrations of the hydrated proton complex. Broadband ultrafast two-dimensional IR spectroscopy and transient absorption are used to measure vibrational relaxation, spectral diffusion, and orientational relaxation dynamics. The hydrated proton bend displays fast vibrational relaxation and spectral diffusion timescales of 200–300 fs; however, the transient absorption anisotropy decays on a remarkably long 2.5 ps timescale, which matches the timescale for hydrogen bond reorganization in liquid water. These observations are indications that the bending vibration of the aqueous proton complex is relatively localized, with an orientation that is insensitive to fast hydrogen bonding fluctuations and dependent on collective structural relaxation of the liquid to reorient. Here, we conclude that the orientational relaxation is a result of proton transfer between configurations that are well described by a Zundel-like proton shared between two flanking water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Bulk-like and Interfacial Water Dynamics in Nafion Fuel Cell Membranes Investigated with Ultrafast Nonlinear IR Spectroscopy

The water confined in the hydrophilic domains of Nafion fuel cell membranes is central to its primary function of ion transport. Water dynamics are intimately linked to proton transfer and are sensitive to the structural features and length scales of confinement. Here, ultrafast polarization-selective pump-probe and two-dimensional infrared vibrational echo (2D IR) experiments were performed on fully hydrated Nafion membranes with sodium counterions to explicate the water dynamics. Like aerosol-OT reverse micelles (AOT RMs), the water dynamics in Nafion are attributed to bulk-like core water in the central region of the hydrophilic domains and much slower interfacial water. Population and orientational dynamics of water in Nafion are slowed by polymer confinement. Comparison of the observed dynamics to those of AOT RMs helps identify local interactions between water and sulfonate anions at the interface and among water molecules in the core. This comparison also demonstrates that the well-known spherical cluster morphology of Nafion is not appropriate. Spectral diffusion of the interfacial water, which arises from structural dynamics, was obtained from the 2D IR experiments taking the core water to have dynamics similar to bulk water. Like the orientational dynamics, spectral diffusion was found to be much slower at the interface compared to bulk water. Together, the dynamics indicate slow reorganization of weakly hydrogen-bonded water molecules at the interface of Nafion. We report these results provide insights into proton transport mechanisms in fuel cell membranes, and more generally, water dynamics near the interface of confining systems.

25 ENERGY STORAGE↗
DOE OSTI2020

Experimental and DFT Calculated IR Spectra of Guests in Zeolites: Acyclic Olefins and Host-Guest Interactions

We performed experimental and periodic density functional theory (DFT) IR spectroscopy to investigate the adsorption of acyclic olefins over both acidic and non-acidic zeolites. Two conjugated polyenes, 2,4-dimethyl-1,3-pentadiene (I) and 2,6-dimethyl-2,4,6-octatriene (II) were studied to probe organic intermediates that can form during methanol conversion, and that can lead to deactivating species known collectively as “coke.” We computed vibrational spectra using zeolite-adsorbed and gas-phase models for both neutral and protonated forms of I and II, and compared these DFT results to diffuse reflectance IR Fourier transform (DRIFT) spectra of zeolite-guest systems. Our experimental and computational results are precise enough to pinpoint that the gauche s-cis conformation of species I predominates during adsorption over de-aluminated zeolite beta. Computed zeolite-adsorbed spectra of the protonated species I and II best represent the DRIFT spectra obtained after the adsorption of the olefins on HMOR at 20 ?, with computed bands at 1543 and 1562 cm–1 for molecules I+ and II+, respectively, attributed to the allylic stretching mode, ?(C=C–C+). These computed band frequencies are within 6 cm–1 of experimental data and confirm that the interaction between neutral acyclic olefins and acidic zeolites leads to protonation of the olefin. Comparison of computed spectra of the protonated species in the gas phase to those in the zeolite indicates that the electrostatic interaction between alkenyl and alkadienyl cations and negative zeolite framework does not significantly impact the position of the allylic stretching bands. These results highlight that computed spectroscopy and thermodynamics coupled with experimental spectra can be used for elucidating complex mixtures in zeolites, and certain spectral features of adsorbed olefins can be accurately modeled by gas-phase calculations. ACKNOWLEDGMENTS BM and SMA were supported by the National Science Foundation under Award # CBET-1512442. Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund for support (or partial support) of this research (#589978-ND5, EDH and FCJ). MDB was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences (BES), Division of Materials Science and Engineering. CJM was supported by the DOE, Office of Science, BES, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated by Battelle for the U.S. DOE. Computing resources were generously provided through PNNL’s institutional computing (PIC).

Manookian, Babgen↗
DOE OSTI2024

Unveiling the Role of Surface Ir-Oxo Species in O 2 Evolution at IrO 2 Electrocatalysts via Embedded Cluster Multireference Calculations

Understanding the mechanisms driving the oxygen evolution reaction (OER) on iridium oxide (IrO 2 )-based catalysts is essential to improving their performance and enabling an actual scale-up of water-splitting photoelectrochemical cells. The mechanistic pathways at IrO 2 interfaces have been extensively investigated computationally using density functional theory (DFT), which predicts a high-energy barrier for the last step of the OER of molecular oxygen detachment and release from the catalyst surface. Nevertheless, surface O 2 over- and under-binding results by standard generalized gradient approximation and hybrid density functionals, respectively, call for further analysis of this crucial step via multireference methods. Aiming at unveiling the nature of such a barrier, we hereby address the formation of O 2 from the most-stable IrO 2 (110) surface with both periodic DFT and an electrostatic embedded cluster approach at the n-electron valence-state perturbation theory. With this multireference approach, we find a value for the aforementioned energy barrier that is much closer to experimental indications than DFT ones. Here, an in-depth analysis of the involved molecular orbitals suggests that the origin of this barrier is related to the breaking of a π interaction between O 2 and Ir surface atom and to a significant additional O 2 interaction with adjacent electrophilic Ir-oxo species, which is present under experimental operating conditions. Besides shedding light on the mechanism of the OER on IrO 2 , these findings point out the importance of multireference methods for dissecting complex reactions at electrocatalytic interfaces and pave the route for further investigations with effective embedding approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Single-Phase Pyrochlore Y 2 Ir 2 O 7 Electrocatalyst on the Activity of Oxygen Evolution Reaction

Single phase pyrochlore-type Y 2 Ir 2 O 7 electrocatalyst was made through the sol-gel synthesis. This catalyst has high activity and stability towards oxygen evolution reaction (OER) in acid. Here, chronopotentiometry analysis showed no obvious change in overpotential for more than 24 h measurement at 10 mA/cm 2 geo . X-ray absorption spectroscopy (XAS) demonstrates that the single electron filling in e" orbital of Ir 5d states, induced by the spin-orbital coupling, could contribute to the improved OER activity.

36 MATERIALS SCIENCE↗
DOE OSTI2021

3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis

Atomically dispersed metal catalysts are hailed as the most promising catalyst category for oxygen electrocatalysis. However, the challenges in regulating electronic configuration and unveiling the mechanism on the atomic scale are hindering their practical implementation. Herein, we modulate the Co d-orbital electron configuration by constructing the Ir–Co atomic pair toward boosted bifunctional activity. The as-developed dual-atom IrCo–N–C catalyst displays unprecedented activity with a half-wave potential of 0.911 V for oxygen reduction reaction and only 330 mV overpotential at 10 mA cm –2 for oxygen evolution reaction, outperforming the single-atom counterparts as well as the commercial Pt/C and Ir/C benchmarks. The impressive bifunctionality is also verified in a Zn–air battery prototype with an ultra-high cyclability over 450 cycles. Furthermore, theoretical calculations are performed to shed light on the synergetic effects of the atomic pair site, where the incorporation of Ir atom alters the d-orbital energy level of Co and thus induces the re-arrangement of d-electron toward intensified spin polarization. As a result, the lower occupancy of d z 2 orbital facilitates the electron acceptation from oxygen to form a stronger Co–O σ bond, thereby propelling faster reaction kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Stable Platinum(IV) Corroles: Synthesis, Molecular Structure, and Room-Temperature Near-IR Phosphorescence

A series of stable Pt(IV) corrole complexes with the general formula Pt IV [TpXPC](m/p-C 6 H 4 CN)(py), where TpXPC 3- is the trianion of a tris(p-X-phenyl)corrole and X = CF 3 , H, and CH 3 , has been synthesized, affording key physicochemical data on a rare and elusive class of metallocorroles. Single-crystal X-ray structures of two of the complexes revealed very short equatorial Pt-N distances of 1.94-1.97 Å, an axial Pt-C distance of ~2.03 Å, and an axial Pt-N distance of ~2.22 Å. The complexes exhibit Soret maxima at ~430 nm, which are essentially independent of the meso-aryl para substituents, and strong Q bands with the most intense peak at 595-599 nm. The substituent-independent Soret maxima are consistent with an innocent Pt IV -corrole 3 - description for the complexes. The low reduction potentials (-1.45 ± 0.08 V vs saturated calomel reference electrode) also support a highly stable Pt(IV) ground state as opposed to a noninnocent corrole •2- description. The reductions, however, are irreversible, which suggests that they involve concomitant cleavage of the Pt-aryl bond. Unlike Pt(IV) porphyrins, two of the complexes, Pt IV [TpXPC](m-C 6 H 4 CN)(py) (X = CF 3 and CH 3 ), were found to exhibit room-temperature near-IR phosphorescence with emission maxima at 813 and 826 nm, respectively. Finally, the quantum yield of ~0.3% is comparable to those observed for six-coordinate Ir(III) corroles.

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

PCET-Based Ligand Limits Charge Recombination with an Ir(III) Photoredox Catalyst

Upon photoinitiated electron transfer, charge recombination limits the quantum yield of photoredox reactions for which the rates for the forward reaction and back electron transfer are competitive. Taking inspiration from a proton-coupled electron transfer (PCET) process in Photosystem II, here a benzimidazole-phenol (BIP) has been covalently attached to the 2,2'-bipyridyl ligand of [Ir(dF(CF 3 )ppy) 2 (bpy)][PF 6 ] (dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; bpy = 2,2'-bipyridyl). Excitation of the [Ir(dF(CF 3 )ppy) 2 (BIP-bpy)][PF 6 ] photocatalyst results in intramolecular PCET to form a charge-separated state with oxidized BIP. Subsequent reduction of methyl viologen dication (MV 2+ ), a substrate surrogate, by the reducing moiety of the charge separated species demonstrates that the inclusion of BIP significantly slows the charge recombination rate. The effect of ~24-fold slower charge recombination in a photocatalytic phthalimide ester reduction resulted in a greater than 2-fold increase in reaction quantum efficiency.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Synthesis and Characterization of Core-Shell Cu-Ru, Cu-Rh, and Cu-Ir Nanoparticles

Optimizing the use of expensive precious metals is critical to developing sustainable and low-cost processes for heterogeneous catalysis or electrochemistry. Here, we report a synthesis method that yields core-shell Cu-Ru, Cu-Rh, and Cu-Ir nanoparticles with the platinum-group metals segregated on the surface. The synthesis of Cu-Ru, Cu-Rh, and Cu-Ir particles allows maximization of the surface area of these metals and improves catalytic performance. Furthermore, the Cu core can be selectively etched to obtain nanoshells of the platinum-group metal components, leading to a further increase in the active surface area. Characterization of the samples was performed with X-ray absorption spectroscopy, X-ray powder diffraction, and ex situ and in situ transmission electron microscopy. CO oxidation was used as a reference reaction: the three core-shell particles and derivatives exhibited promising catalyst performance and stability after redox cycling. Furthermore, these results suggest that this synthesis approach may optimize the use of platinum-group metals in catalytic applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Aqueous Cation-Amide Binding: Free Energies and IR Spectral Signatures by Ab Initio Molecular Dynamics

Understanding specific ion effects on proteins remains a considerable challenge. N-methylacetamide serves as a useful proxy for the protein backbone that can be well characterized both experimentally and theoretically. The spectroscopic signatures in the amide I band reflecting the strength of the interaction of alkali cations and alkali earth dications with the carbonyl group remain difficult to assign and controversial to interpret. Herein, we directly compute the IR shifts corresponding to the binding of either sodium or calcium to aqueous N-methylacetamide using ab initio molecular dynamics simulations. We show that the two cations interact with aqueous N-methylacetamide with different affinities and in different geometries. Since sodium exhibits a weak interaction with the carbonyl group, the resulting amide I band is similar to an unperturbed carbonyl group undergoing aqueous solvation. In contrast, the stronger calcium binding results in a clear IR shift with respect to N-methylacetamide in pure water. Support from the Czech Ministry of Education (grant LH12001) is gratefully acknowledged. EP thanks the International Max-Planck Research School for support and the Alternative Sponsored Fellowship program at Pacific Northwest National Laboratory (PNNL). PJ acknowledges the Praemium Academie award from the Academy of Sciences. Calculations of the free energy profiles were made possible through generous allocation of computer time from the North-German Supercomputing Alliance (HLRN). Calculations of vibrational spectra were performed in part using the computational resources in the National Energy Research Supercomputing Center (NERSC) at Lawrence Berkeley National Laboratory. This work was supported by National Science Foundation grant CHE-0431312. CJM is supported by the U.S. Department of Energy`s (DOE) Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. PNNL is operated for the Department of Energy by Battelle. MDB is grateful for the support of the Linus Pauling Distinguished Postdoctoral Fellowship Program at PNNL.

calcium↗
DOE OSTI2017

Fluorine substituted (Mn,Ir)O 2 :F high performance solid solution oxygen evolution reaction electro-catalysts for PEM water electrolysis

Identification and development of high performance with reduced overpotential (i.e. reduced operating electricity cost) oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane (PEM) based water electrolysis with ultra-low noble metal content (i.e. reduced materials cost) is of significant interest for economic hydrogen production, thus increasing the commercialization potential of PEM water electrolysis. Accordingly, a novel electrocatalyst should exhibit low overpotential, excellent electrochemical activity and durability superior to state of the art noble metal based electro-catalysts (e.g. Pt, IrO 2 , RuO 2 ). Here in this paper, for the very first time to the best of our knowledge, exploiting first-principles theoretical calculations of the total energies and electronic structures, we have identified a reduced noble metal content fluorine doped solid solution of MnO 2 and IrO 2 , denoted as (Mn 1-x Ir x )O 2 :F (x = 0.2, 0.3, 0.4), OER electrocatalyst system exhibiting lower overpotential and higher current density than the state of the art IrO 2 and other previously reported systems for PEM water electrolysis. The doped solid solution displays an excellent electrochemical performance with a lowest reported onset potential to date of ~1.35 V (vs. RHE), ~80 mV lower than that of IrO 2 (~1.43 V vs. RHE) and ~15 fold (x = 0.3 and 0.4) higher electrochemical activity compared to pure IrO 2 . In addition, the system displays excellent long term electrochemical durability, similar to that of IrO 2 in harsh acidic OER operating conditions. Our study therefore demonstrates remarkable, ~60–80% reduction in noble metal content along with lower overpotential and excellent electrochemical performance clearly demonstrating the potential of the (Mn 1-x Ir x )O 2 :F system as an OER electro-catalyst for PEM water electrolysis.

08 HYDROGEN↗
DOE OSTI2018

Novel N 6 trisbidentate ligand coordinated Ir( III ) complexes and their Ru( II ) analogs

In this work, novel N 6 -coordinated Ir( III ) complexes bearing polypyridyl ligands were synthesized and characterized. In comparison to their Ru( II ) analogs, these Ir( III ) complexes showed blue-shifted UV-vis absorption and emission spectra, but dramatically increased triplet lifetimes with much broader and stronger triplet excited-state absorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗