Search NASA⌕ Search

SEARCH · Search NASA

Results for “Molecular 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.

At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Dual atom catalysts for rapid electrochemical reduction of CO to ethylene

Strong CO adsorption and facile CO dimerization are the key challenges in electrochemical CO2 reduction towards multi-carbon (C2+) products. We recently showed that CoPc immobilized on a single-walled carbon nanotube can selectively reduce CO2 to methanol. This is enabled through molecular strain, which dramatically improves the CO adsorption energy to CoPc, which in turn facilitates methanol formation. We now examine the extended Phthalocyanine (PcEx) dual atom catalyst (DAC), which is intrinsically strained and contains two catalyst centers, making it a candidate for reducing CO to C2+ products. Using Quantum Mechanics (QM), we screened 20 elements embedded in the PcEx, seeking catalysts with weak hydrogen binding, strong CO binding, and facile CO dimerization. We identi>ied Fe, Ru, Co, and Ir as the best performers and subsequently evaluated the entire CO to C2H4 mechanism (9 steps) using each of these elements as catalysts. In terms of limiting potential and overall exergonicity, we identi>ied CoPcEx as the best catalyst, followed by IrPcEx. We then examined the full CO to C2H4 mechanism on the bimetallic IrCoPcEx catalyst using grand canonical QM to obtain the reaction energetics as a function of applied potential. We conclude that the bimetallic IrCoPcEx is most promising for ef>iciently converting CO to ethylene.

Musgrave, Charles B.↗
DOE OSTI2021

An Asymmetric Dust Ring around a Very Low Mass Star ZZ Tau IRS

We present Atacama Large Millimeter/submillimeter Array (ALMA) gas and dust observations at band 7 (339 GHz: 0.89 mm) of the protoplanetary disk around a very low mass star ZZ Tau IRS with a spatial resolution of 025. The {sup 12}CO J = 3 → 2 position–velocity diagram suggests a dynamical mass of ZZ Tau IRS of ∼0.1–0.3 M {sub ☉}. The disk has a total flux density of 273.9 mJy, corresponding to an estimated mass of 24–50 M {sub ⊕} in dust. The dust emission map shows a ring at r = 58 au and an azimuthal asymmetry at r = 45 au with a position angle of 135°. The properties of the asymmetry, including radial width, aspect ratio, contrast, and contribution to the total flux, were found to be similar to the asymmetries around intermediate mass stars (∼2 M {sub ☉}) such as MWC 758 and IRS 48. This implies that the asymmetry in the ZZ Tau IRS disk shares a similar origin with others, despite the star being ∼10 times less massive. Our observations also suggest that the inner and outer parts of the disk may be misaligned. Overall, the ZZ Tau IRS disk shows evidence of giant planet formation on a ∼10 au scale at a few megayears. If confirmed, it will challenge existing core accretion models in which such planets have been predicted to be extremely hard to form around very low mass stars.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Electrokinetic comparison of CaF 2 and AgCl from a MDS perspective

CaF 2 has limited electrokinetic sensitivity to fluoride ions in solution and the positive CaF 2 surface charge is not reversed at high fluoride ion concentration. Similar insensitivity of surface charge to high fluoride ion concentration has been observed for other alkali and alkaline earth fluoride salts. On the contrary, chloride ions act as potential determining ions for AgCl and reverse the surface charge, as expected. FTIR-IRS results indicate that the AgCl/water interface has a water structure-breaking tendency, whereas the CaF 2 /water interface has a structure-making tendency. Here, it is speculated that the strong hydrogen bonding between fluoride ions and water prevents the accommodation of excess fluoride ions at surface lattice sites of fluorite, and therefore explains the low sensitivity of the fluorite surface charge sign and magnitude to fluoride ion concentration. However, this speculation has not been examined at the molecular level and is evaluated by molecular dynamics simulations (MDS) in the research presented in this paper. Higher hydrogen bond density at the CaF 2 mineral/water interface confirms that the water structure has stronger hydrogen bonding at both the CaF 2 mineral surface and with the F - ion in solution. In this way, the interaction of the F - ion with the CaF 2 surface is inhibited.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Probing ultrafast excited-state dynamics using EUV-IR six-wave-mixing emission spectroscopy

Non-linear processes such as four-wave-mixing have become instrumental in attosecond EUV spectroscopy. Using EUV high harmonics in conjunction with collinear near-infrared and mid-infrared fields, we extended this approach to high-order-mixing between three colors. Specifically, we find that atomic resonances in neon exhibit a significant cross section for six-wave mixing. The MIR probe frequency tunability in our multicolor scheme is employed to access several optically dark resonances and probe the quantum beat of a coherent electronic wavepacket using background-free EUV emission as a diagnostic. This technique can be easily extended to other atomic and molecular systems, and opens the door to multi-dimensional non-linear spectroscopy.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Ethanol Upgrading to n -Butanol Using Transition-Metal-Incorporated Poly(triazine)imide Frameworks

The upgrading of ethanol to n-butanol was performed using a molecular catalyst integrated into a carbon nitride support, one of the first examples of a supported molecular catalyst performing the Guerbet process. Initial studies using crystalline poly(triazine)imide (PTI) with lithium or transition-metal cations imbedded in the support together with a base as the catalyst system did not produce any significant amounts of n-butanol. However, when using the catalyst material formed by treatment of PTI-LiCl with [(Cp*)IrCl 2 ] 2 (Cp* = pentamethylcyclopentadienyl) along with sodium hydroxide, a 59% selectivity for butanol (13% yield) was obtained at 145 °C. This PTI-(Cp*)Ir material exhibited distinct UV–vis absorption features and powder X-ray diffractions which differ from those of the parent PTI-LiCl and [(Cp*)IrCl 2 ] 2 . Here, the PTI-(Cp*)Ir material was found to have a metal loading of 27% iridium per empirical unit of the framework. Along with the formation of n-butanol from the Guerbet reaction, the presence of higher chain alcohols was also observed.

Guerbet↗
DOE OSTI2024

Determining the Effects of Zero-Field Splitting and Magnetic Exchange in Dimeric Europium(II) Complexes

Related BAP [BAP = bis(acyl)phosphide] and Acac (Acac = β-diketonate) molecules perform as robust supports for both lanthanide and actinide metals. Here, a molecular bimetallic Eu 2+ complex was successfully targeted and isolated by employing sodium bis(mesitoyl)phosphide [Na( mes BAP)] in a salt metathesis with EuI 2 , producing [Eu( mes BAP) 2 (et 2 o)] 2 (et 2 o = metal-coordinated diethyl ether). The corresponding Acac-Eu 2+ complex was targeted using mes Acac– (1,3-dimesityl-1,3-propanedione), generating [Eu( mes Acac) 2 (et 2 o)] 2 . Both complexes were characterized by single-crystal X-ray diffraction, UV–vis, IR, and NMR spectroscopies, and variable-temperature magnetic susceptibility. [Eu( mes BAP) 2 (et 2 o)] 2 was persistent under anaerobic, anhydrous conditions, whereas the analogous [Eu( mes Acac) 2 (et 2 o)] 2 showed evidence of decomposition under identical conditions. Finally, variable-temperature magnetic susceptibility and magnetization studies of [Eu( mes BAP) 2 (et 2 o)] 2 and [Eu( mes Acac) 2 (et 2 o)] 2 were performed, resulting in similar magnetic exchange coupling values of J ex = –0.018 and –0.023 cm –1 and axial zero-field-splitting D values of –0.38 and –0.51 cm –1 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Weakening the N–H Bonds of NH 3 Ligands: Triple Hydrogen-Atom Abstraction to Form a Chromium(V) Nitride

Weakening and cleaving N-H bonds is crucial for improving molecular ammonia oxidation catalysts. In this work, we report the synthesis and hydrogen atom abstraction chemistry of bis(ammonia) Cr porphyrin complexes Cr(TPP)(NH 3 ) 2 and Cr(TMP)(NH 3 ) 2 (TPP = 5,10,15,20-tetraphenyl-meso-porphyrin and TMP = 5,10,15,20-tetramesityl-meso-porphyrin) using bulky aryloxyl radicals. The triple hydrogen atom abstraction reaction results in the formation of Cr V (por)(≡N), with the nitride deriving from ammonia, as indicated by UV-Vis and FT-IR spectroscopy, and a single crystal structural determination of Cr(TPP)(≡N). Subsequent oxidation of this chromium(V)-nitrido complex results in the formation of Cr III (por), with scission of the Cr≡N bond. A computational analysis illustrates the progression from Cr II to Cr V and evaluates the energetics of abstracting hydrogen atoms from Cr II -NH 3 to generate Cr V ≡N. The formation and isolation of Cr V (por)(≡N) illustrates the stability of these species and the need to chemically activate the nitride moiety for atom transfer or N-N coupling reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Disentangling the chemistry of Australian plant exudates from a unique historical collection

For thousands of years, the unique physicochemical properties of plant exudates have defined uses in material culture and practical applications. Native Australian plant exudates, including resins, kinos, and gums, have been used and continue to be used by Aboriginal Australians for numerous technical and cultural purposes. A historic collection of well-preserved native Australian plant exudates, assembled a century ago by plant naturalists, gives a rare window into the history and chemical composition of these materials. Here we report the full hierarchical characterization of four genera from this collection, Xanthorrhoea, Callitris, Eucalyptus, and Acacia, from the local elemental speciation, to functional groups and main molecular markers. We use high-resolution X-ray Raman spectroscopy (XRS) to achieve bulk-sensitive chemical speciation of these plant exudates, including insoluble, amorphous, and cross-linked fractions, without the limitation of invasive and/or surface specific methods. Combinatorial testing of the XRS data allows direct classification of these complex natural species as terpenoid, aromatic, phenolic, and polysaccharide materials. Differences in intragenera chemistry was evidenced by detailed interpretation of the XRS spectral features. We complement XRS with Fourier-transform infrared (FT-IR) spectroscopy, gas chromatography–mass spectrometry (GC-MS), and pyrolysis–GC-MS (Py-GC-MS). This multimodal approach provides a fundamental understanding of the chemistry of these natural materials long used by Aboriginal Australian peoples.

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

Slow-Light Mid-IR Silicon Photonic Chips for NO 2 and CH 4 Gas Detection

A compact, chip-scale mid-infrared gas sensor is demonstrated, leveraging a two-dimensional photonic crystal waveguide (PCW) fabricated on a silicon-on-insulator (SOI) platform. The PCW comprises a hexagonal lattice with lattice constant a = 860 nm and hole radius r = 0.22a, incorporating a central line defect of reduced-radius holes (r s = 0.7r) to induce slow-light propagation near the photonic band edge with a group index of approximately 73, thereby enhancing light-matter interaction. The sensor operates at fundamental absorption wavelengths of 3.42 μm for nitrogen dioxide (NO 2 ) and 3.40 μm for methane (CH 4 ), utilizing the strongest molecular vibrational transitions for maximum sensitivity. Experimental validation was conducted using dynamically diluted gas mixtures generated by mass flow controllers, with signal acquisition performed by a liquid nitrogen-cooled InSb detector. For NO 2 , the sensor exhibited excellent linear response over 5–25 ppm (part per million) with coefficient of determination R 2 = 0.9934, achieving a detection limit of 210 ppb (part per billion)─representing the first reported silicon photonic-based NO 2 detection. For CH 4 , exposure to 25 ppm resulted in a 6.4% decrease in transmitted intensity, demonstrating multigas sensing capability. The CMOS-compatible fabrication process and compact 3 mm device footprint establish this SOI-PCW platform as a scalable, low-power solution for integrated mid-infrared gas sensing, with significant potential for environmental monitoring and industrial safety applications.

Crystals↗
DOE OSTI2025

Fano Resonance in CO 2 Reduction Catalyst Functionalized Quantum Dots

Molecular catalyst functionalized semiconductor quantum dots (QDs) are a promising modular platform for developing novel hybrid photocatalysts. The interaction between adsorbed catalyst vibrations and the QD electron intraband absorption can influence the photophysical properties of both the QD and the catalysts and potentially their photocatalysis. In CdSe QDs functionalized by the CO 2 reduction catalyst, Re(CO) 3 (4,4’-bipyridine-COOH)Cl, we observe that the transient Fano resonance signal resulting from coupling of the catalyst CO stretching mode and the QD conduction band electron mid-IR intraband absorption appears on an ultrafast time scale and decays with the electron population, irrespective of the occurrence of photoreduced catalysts. The Fano asymmetry factor increases with an increase in the adsorbed catalyst number and a decrease in QD sizes. The latter can be attributed to an enhanced charge transfer interaction between the more strongly quantum-confined QD conduction band and catalyst LUMO levels. These results provide a more in-depth understanding of interactions in excited QD-catalyst hybrid photocatalysts.

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

Molecular chemisorption of N 2 on IrO 2 (110)

We investigated the adsorption of N 2 on stoichiometric and O-rich IrO 2 (110) surfaces using temperature programmed desorption (TPD) experiments and density functional theory (DFT) calculations. TPD shows that N 2 desorbs predominantly from the stoichiometric-IrO 2 (110) surface in a well-defined peak at 270 K for N 2 coverages below about 0.5 ML, and that a shoulder centered near 235 K develops in the N 2 TPD traces as the coverage approaches saturation, indicating that adsorbed N 2 molecules become destabilized at high N 2 coverage. Experiments of N 2 adsorption onto O-rich IrO 2 (110) surfaces provide evidence that N 2 adsorbs exclusively on the coordinatively-unsaturated Ir atoms (Ircus) of the surface, and that pre-adsorbed O-atoms (“on-top” oxygen) stabilize adsorbed N 2 molecules, causing the main N 2 TPD peak to shift toward higher temperature with increasing oxygen coverage. Consistent with prior results, our DFT calculations predict that an N 2 molecule preferentially adsorbs into an upright configuration on an Ircus atom of the IrO 2 (110) surface and achieves a binding energy of about 100 kJ/mol. The computed binding energy agrees well with our experimental estimate of ~90 kJ/mol for low N 2 coverages on stoichiometric IrO 2 (110). Lastly, the DFT calculations also quantitatively reproduce the observed stabilization of N 2 by co-adsorbed on-top O-atoms and predict the destabilization of N 2 on IrO 2 (110) as the N 2 adlayer becomes crowded at high coverage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Characterization of single-shot attosecond pulses with angular streaking photoelectron spectra

Most of the traditional attosecond pulse retrieval algorithms are based on a so-called attosecond streak camera technique, in which the momentum of the electron is shifted by an amount depending on the relative time delay between the attosecond pulse and the streaking infrared pulse. Thus, temporal information of the attosecond pulse is encoded in the amount of momentum shift in the streaked photoelectron momentum spectrogram S(p,τ), where p is the momentum of the electron along the polarization direction and τ is the time delay. An iterative algorithm is then employed to reconstruct the attosecond pulse from the streaking spectrogram. This method, however, cannot be applied to attosecond pulses generated from free-electron x-ray lasers where each single shot is different and stochastic in time. However, using a circularly polarized infrared laser as the streaking field, a two (or three)-dimensional angular streaking electron spectrum can be used to retrieve attosecond pulses for each shot, as well as the time delay with respect to the circularly polarized IR field. Here we show that a retrieval algorithm previously developed for the traditional streaking spectrogram can be modified to efficiently characterize single-shot attosecond pulses. The methods have been applied to retrieve 188 single shots from recent experiments. We analyze the statistical behavior of these 188 pulses in terms of pulse duration, bandwidth, pulse peak energy, and time delay with respect to the IR field. Furthermore, the retrieval algorithm is efficient and can be easily used to characterize a large number of shots in future experiments for attosecond pulses at free-electron x-ray laser facilities.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

N-Heterocyclic Carbene Complexes of Nickel, Palladium, and Iridium Derived from Nitron: Synthesis, Structures, and Catalytic Properties

Nitron, has been employed as a “crypto-N-heterocyclic carbene” to afford 1,2,4-triazolylidene compounds of nickel, palladium and iridium. Significantly, the ligand derived from Nitron, namely Nitron NHC , affords catalytic systems, as illustrated by the ability of the iridium compound (Nitron NHC )Ir(CO) 2 Cl to effect (i) dehydrogenation of formic acid, (ii) aldehyde hydrosilyation, (iii) dehydrocoupling of hydrosilanes and alcohols, and (iv) ketone reduction via transfer hydrogenation.

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

Solvated Ionic Liquid-based Electrolytes: Experimental Characterization, Atomistic Modeling and Applications in Energy Storage

This study aimed on understanding the molecular structure and transport mechanisms of high-concentration lithium electrolytes, with a particular focus on solvate ionic liquids (SILs) based on glyme solvents, for use in next-generation, high-voltage energy storage systems. The hypothesis is that the composition of the solvents in these electrolytes can be designed and adjusted to control cation solvation, enabling charge transport via an ion-hopping mechanism. This mechanism resembles Grotthuss conduction of protons in water and is independent of electrolyte viscosity. The experimental studies employed linear and nonlinear infrared spectroscopy (FTIR and 2D IR), electrochemical measurements, and vibrational probes.

25 ENERGY STORAGE↗
DOE OSTI2025

Dicopper( i ) complexes of a binucleating, dianionic, naphthyridine bis(amide) ligand

The dinucleating ligand, 1,8-naphthyridine-2,7-bis(2,6-diisopropylphenyl)carboxamide (NBDA), was synthesized by palladium-catalyzed aminocarbonylation. This ligand was treated with two equivalents of mesitylcopper(I) in the presence of [nBu4N]X (X = Cl, N3) to give the anionic complexes [nBu4N][Cu2(NBDA)(μ-Cl)] and [nBu4N][Cu2(NBDA)(μ-N3)]. Treatment of H2NBDA with mesitylcopper(I) and two equivalents of xylyl isocyanide led to the formation of a charge-neutral dicopper(I) complex, [Cu2(NBDA)(CNXyl)2], displaying two isocyanide ligands, each terminally bound to one of the copper atoms. The complexes were characterized by NMR and IR spectroscopy, as well as by single-crystal X-ray diffraction analysis. Electrochemical characterization of the complexes using cyclic voltammetry revealed a reversible ligand-based reduction between -1.65 and -2.0 V vs. Fc/Fc+. DFT calculations suggest a more ionic bonding character and weaker Cu-Cu interactions in the NBDA complexes compared to those with other 1,8-naphthyridine-based ligands. This is congruent with intermetallic separations of over 3 Å induced by relatively strong coordination of the copper atoms to the amide nitrogen donor atoms observed in the solid state molecular structures.

Sévery, Laurent↗
DOE OSTI2023

High-entropy halide perovskite single crystals stabilized by mild chemistry

High entropy materials are excellent candidates for a range of functional materials but traditionally require high-temperature synthetic procedures over 1000°C and complex processing techniques such as hot rolling to form. One route to address the extreme synthetic requirements for high entropy materials should involve designing crystal structures with ionic bonding networks and low cohesive energies. Here, we develop room-temperature (20°C) and low temperature (80°C) solution synthesis procedures for a new class of metal-halide perovskite high entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of the class of metal-halide perovskites, these HES single crystals are designed on the cubic Cs 2 MCl 6 (M = Zr 4+ , Sn 4+ , Te 4+ , Hf 4+ , Re 4+ , Os 4+ , Ir 4+ , or Pt 4+ ) vacancy-ordered double perovskite structure from the self-assembly of stabilized complexes in multielement inks, namely free Cs + cations and five or six different isolated [MCl6] 2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five- and six-elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs 2 MCl 6 crystal structure and stoichiometry maintained. In conclusion, the incorporation of various [MCl 6 ] 2- octahedral molecular orbitals disordered across the high entropy five- and six-element Cs 2 MCl 6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Magnetism Studies of Bis(acyl)phosphide-Supported Eu 3+ and Eu 2+ Complexes

A series of bis(acyl)phosphide-supported Eu complexes were synthesized (bis(acyl)phosphide = BAP). Here, in this study, BAP ligands proved to be excellent ligands for the synthesis of both Eu 3+ and Eu 2+ molecular complexes. Sodium bis(mesitoyl)phosphide (Na( mes BAP)) and sodium bis(2,4,6-triisopropylbenzoyl)phosphide (Na( tripp BAP)) were employed as ligand precursors for the synthesis of the Eu 3+ complexes Eu(bis(mesitoyl)phosphide) 3 (thf) 2 (Eu( mes BAP) 3 (thf) 2 ) and Eu(bis(2,4,6-triisopropylbenzoyl)phosphide) 3 (Eu( tripp BAP) 3 ), as well as the Eu 2+ complex, Eu(bis(2,4,6-triisopropylbenzoyl)phosphide) 2 (dme) 2 (Eu( tripp BAP) 2 (dme) 2 ) (thf = tetrahydrofuran, dme = 1,2-dimethoxyethane). All complexes were characterized using a combination of UV–vis–NIR–IR and NMR spectroscopies, and single-crystal X-ray diffraction (SC-XRD). The magnetic properties of these three monomeric Eu complexes were investigated by variable-temperature magnetic susceptibility. The magnetic data are typical for these ions, with Eu( tripp BAP) 2 (dme) 2 displaying Curie-type behavior. Both Eu( tripp BAP) 3 and Eu( mes BAP) 3 (thf) 2 possess similar 7 F 0 - 7 F 1 spin–orbit energy gaps and a similar zero-field splitting of the 7 F 1 state.

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

Direct Synthesis of Polyester from Biomass Derived 1,6-hexanediol using a Copper-Ceria Catalyst

Biomass derived polyesters are gaining attention due to their increased mechanical and thermal properties, and also because of their biodegradability. These polyesters are typically synthesized from polycondensation reactions between diols with dicarboxylic acids using catalysts. Other methods such as alcoholysis and acidolysis of low molecular weight esters and alcoholysis of acyl chlorides are also well known. Direct conversion of diol to ester without using dicarboxylic acid is not well known, and to our knowledge has not been reported over a solid catalyst. In this study, we report a direct synthesis of polyester from 1,6-hexanediol using a copper-ceria catalyst without using a dicarboxylic acid monomer. The copper-ceria catalysts were synthesized by incipient wetness impregnation method and characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller (BET), and infrared spectroscopy (IR). Our initial studies show that 1,6-hexanediol can be converted to corresponding polyester at higher temperatures under atmospheric pressures of CO2 or N2. The reaction products were analyzed using nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), and IR spectroscopy.

Biomass derived diols↗