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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Long interior carrier lifetime in selective-area InAs nanowires on silicon

Catalyst-free, position-controlled indium arsenide (InAs) nanowires (NWs) of variable diameters were grown on Si (111) by selective-area epitaxy (SAE). Ultrafast pump-probe spectroscopy was conducted, from which carrier recombination mechanisms on the NW surface and interior were resolved and characterized. NWs grown using SAE demonstrated high optical quality, showing minority carrier lifetimes more than two-fold longer than that of the randomly-positioned (RP) NWs. The extracted SAE-InAs NW interior recombination lifetime was found to be as long as 7.2 ns , 13X longer than previous measurements on RP-NWs; and the surface recombination velocity 4154 cm · s - 1 . Transmission electron microscopy revealed a high density of stacking defects within the NWs, suggesting that interior recombination lifetime can be further increased by improving NW interior crystalline quality.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Dehydrogenation of Propane and n -Butane Catalyzed by Isolated PtZn 4 Sites Supported on Self-Pillared Zeolite Pentasil Nanosheets

Propene and 1,3-butadiene are important building-block chemicals that can be produced by dehydrogenation of propane and butane over Pt catalysts. The challenge is to develop highly active and selective catalysts that are resistant to deactivation by Pt sintering and coke formation. We have recently shown that these objectives can be met for propane dehydrogenation using atomically dispersed Pt atoms anchored to neighboring ≡SiOZn-OH groups bonded to the framework dealuminated zeolite BEA. In the present study, we demonstrate that significantly superior performance can be achieved by using self-pillared pentasil (SPP) zeolite nanosheets. Following catalyst reduction in H 2 , atomic-resolution, scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) indicate that Pt is stabilized in structures well approximated as (≡Si-O-Zn) 4-5 Pt. These species are highly active, selective, and stable for propane dehydrogenation (PDH) to give propene and for n-butane dehydrogenation (BDH) to give 1,3-butadiene. No catalyst deactivation was observed after 12 days of time on stream, and the selectivity remained at nearly 100% for PDH conducted at 823 K and a weight hourly space velocity (WHSV) of 1,350 h -1 . The apparent rate coefficient for PDH over this catalyst is significantly higher than that reported previously for Pt-containing catalysts. For BDH at 823 K and a WHSV of 3560 h -1 , the selectivity to butene isomers and 1,3-butadiene is 98.9%, and the selectivity to 1,3-butadiene is 45%. Here, we propose that the high catalyst stability observed during PDH and BDH is a consequence of a large fraction of the Pt-containing centers being located on the external surface of the zeolite nanosheets, where nascent coke precursors can desorb before condensing to form coke.

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

Ultradoping Boron on Si(100) via Solvothermal Chemistry

Ultradoping introduces unprecedented dopant levels into Si, which transforms its electronic behavior and enables its use as a next-generation electronic material. Commercialization of ultradoping is currently limited by gas-phase ultra-high vacuum requirements. Solvothermal chemistry is amenable to scale-up. However, an integral part of ultradoping is a direct chemical bond between dopants and Si, and solvothermal dopant-Si surface reactions are not well-developed. This work provides the first quantified demonstration of achieving ultradoping concentrations of boron (~1e14 cm 2 ) by using a solvothermal process. Surface characterizations indicate the catalyst cross-reacted, which led to multiple surface products and caused ambiguity in experimental confirmation of direct surface attachment. Density functional theory computations elucidate that the reaction results in direct B-Si surface bonds. Finally, this proof-of-principle work lays groundwork for emerging solvothermal ultradoping processes.

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

Structure and activity of supported bimetallic NiPd nanoparticles: influence of preparation method on CO 2 reduction

Here, bimetallic Ni-Pd and monometallic reference catalysts were prepared by decomposing organometallic precursors, Ni(cod) 2 and Pd 2 (dba) 3 , leading to nanoparticles with sizes ranging from 3 to 6 nm. Two different synthesis procedures were followed: i) solution synthesis using capping ligand (hexadecylamine) followed by impregnation of pre-formed nanoparticles on SiO 2 , called Sol-immobilization (SI); and 2) direct precursor decomposition onto SiO 2 , without stabilizer, called Direct Decomposition (DD). Samples prepared by SI procedure are alloyed bimetallic nanoparticles, whereas samples obtained by DD one show phase segregation. Interestingly, DD samples show better activity for CO 2 hydrogenation into CO (reverse water-gas shift reaction - RWGS) than SI ones. The best compromise between activity for CO 2 activation (at lower temperature) and CO selectivity was achieved with Ni DD and NiPd DD catalysts. Moreover, the addition of palladium increased the concentration of surface undercoordinated sites, which chemisorb CO weakly, thus improving activity and selectivity, in opposition to other samples that chemisorb CO strongly, in multiband configuration. In the presence of Pd, different decomposition rates drive the formation of smaller and more active Ni clusters. The knowledge acquired here on the influence of synthesis conditions on the catalytic properties of Ni-Pd catalysts should guide us to better catalysts for CO 2 transformations into valuable products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

In Situ Neutron Scattering Studies on the Oxidation and Reduction of CeO 2 and Pt–CeO 2 Nanorods

The oxygen vacancy structure of ceria plays a key role in its performance as a favored material for catalysis applications. Here, in this work, we develop an understanding of the effects of Pt loading on the structural evolution of ceria nanorods under redox gas environments that mimic real automotive catalytic converters. In situ neutron scattering studies under redox flow reveal that both CeO 2 and Pt–CeO 2 nanorods share a bulk fluorite structure with the presence of surface Frenkel-type oxygen defects. However, Pt–CeO 2 nanorods are more easily reducible than CeO 2 rods as evidenced by an increased concentration of Ce 3+ , determined by NAP-XPS. Importantly, this work finds no evidence of oxygen vacancy ordered surface reconstruction which has been reported in earlier ex situ investigations. Thus, this work highlights the discrepancy between ex situ and in situ structural observations and emphasizes the need for robust in situ investigations of catalysts to develop industrially relevant materials.

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

Structure–Activity Relationships for Ethanol Dehydrogenation to Acetaldehyde by Silica-Supported Zinc Oxide Catalysts

Silica-supported ZnO efficiently catalyzes the nonoxidative dehydrogenation of ethanol to acetaldehyde, which is relevant for production of 1,3-butadiene from bioethanol. Characterization with in situ spectroscopies under dehydrated conditions (high sensitivity-low energy ion scattering (HS-LEIS), diffuse reflectance (DR) UV–vis, X-ray absorption spectroscopy (XAS), diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS), inelastic neutron scattering (INS), and UV Raman), and ammonia adsorption probed by temperature-programmed desorption followed by DRIFTS and mass spectrometry (DRIFTS-MS NH 3 -TPD), and DFT calculations revealed that the supported ZnO x phase was present as isolated surface ZnO x sites on SiO 2 , with the vast majority coordinated by two siloxane bonds and one silicon atom with two nonbridging oxygens ((≡SiO) 2 Zn 2+ O 2 Si=), anchored at 4-, 5-, and 6-membered siloxane rings. A minor fraction of surface ZnO x sites possessed Lewis acidity, and even fewer sites possessed a Bro̷nsted acidic Zn(OH) + Si moiety. Ethanol temperature-programmed surface reaction-mass spectrometry (TPSR-MS) with various oxidative or ethanol reaction pretreatments indicated that only sites with Lewis and Bro̷nsted acidic character (Zn(OH) + Si) were active for ethanol dehydrogenation, while the majority surface (≡SiO) 2 Zn 2+ O 2 Si= sites were inactive. Greater heterogeneity among all surface ZnO x sites, as assessed by in situ DR UV–vis spectroscopy, was associated with a greater number of ZnO x sites that were active for ethanol dehydrogenation as well as lower enthalpic barriers for acetaldehyde production among the most active surface ZnO x sites. Turnover frequencies and the apparent activation energy for ethanol dehydrogenation were determined from steady-state kinetics. Together, these findings suggested that anchoring inactive surface (≡SiO) 2 Zn 2+ O 2 Si= sites on the silica support caused a greater number of active surface ZnO x sites to adopt a more strained configuration, promoting ethanol dehydrogenation catalysis. Pretreatments and catalysts that promoted desorption of ethanol during TPSR, taken as a marker of surface dehydroxylation, were associated with an increased number of the most active surface (Zn(OH) + Si) sites. Such findings suggested that inactive surface ZnO x sites were activated for ethanol dehydrogenation by dehydroxylation of the support and/or decreased coordination to hemilabile siloxane ligands.

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

Remarkable self-degradation of Cu/SAPO-34 selective catalytic reduction catalysts during storage at ambient conditions

A model Cu/SAPO-34 SCR catalyst with all Cu species maintained as isolated Cu(II) ions is synthesized herein. Following lengthy storage on the shelf under ambient conditions, this catalyst completely and irreversibly deactivates upon any heat treatments above ~100 °C. Via detailed characterizations with surface area/pore volume analysis, XRD, H 2 -TPR, and 27 Al, 29 Si and 31 P solid-state NMR, as well as continuous wave and pulsed EPR studies, it is concluded that over the course of storage, the SCR active sites [Cu(OH)] + and Brønsted acid sites ≡Si-O(H)-Al≡ are attacked by H 2 O molecules trapped in the SAPO-34 framework pores, and undergo hydrolysis to form copper hydroxide and terminal Al sites. Upon thermal treatment, these species interact with each other to form copper-aluminate-like species, leading to irreversible deactivation of this catalyst. This deactivation mechanism does not require or necessarily lead to extensive degradation (i.e., crystallinity loss) of the SAPO-34 support.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Interfacial Connections between Organic Perovskite/n + Silicon/Catalyst that Allow Integration of Solar Cell and Catalyst for Hydrogen Evolution from Water

Abstract The rapidly increasing solar conversion efficiency (PCE) of hybrid organic–inorganic perovskite (HOIP) thin‐film semiconductors has triggered interest in their use for direct solar‐driven water splitting to produce hydrogen. However, application of these low‐cost, electronic‐structure‐tunable HOIP tandem photoabsorbers has been hindered by the instability of the photovoltaic‐catalyst‐electrolyte (PV+E) interfaces. Here, photolytic water splitting is demonstrated using an integrated configuration consisting of an HOIP/n + silicon single junction photoabsorber and a platinum (Pt) thin film catalyst. An extended electrochemical (EC) lifetime in alkaline media is achieved using titanium nitride on both sides of the Si support to eliminate formation of insulating silicon oxide, and as an effective diffusion barrier to allow high‐temperature annealing of the catalyst/TiO 2 ‐protected‐n + silicon interface necessary to retard electrolytic corrosion. Halide composition is examined in the (FA 1‐x Cs x )PbI 3 system with a bandgap suitable for tandem operation. A fill factor of 72.5% is achieved using a Spiro‐OMeTAD‐hole‐transport‐layer (HTL)‐based HOIP/n + Si solar cell, and a high photocurrent density of −15.9 mA cm −2 (at 0 V vs reversible hydrogen electrode) is attained for the HOIP/n + Si/Pt photocathode in 1 m NaOH under simulated 1‐sun illumination. While this thin‐film design creates stable interfaces, the intrinsic photo‐ and electro‐degradation of the HOIP photoabsorber remains the main obstacle for future HOIP/Si tandem PEC devices.

08 HYDROGEN↗
DOE OSTI2020

What fuel properties enable higher thermal efficiency in spark-ignited engines?

The Co-Optimization of Fuels and Engines (Co-Optima) initiative from the US Department of Energy aims to co-develop fuels and engines in an effort to maximize energy efficiency and the utilization of renewable fuels. Many of these renewable fuel options have fuel chemistries that are different from those of petroleum-derived fuels. Because practical market fuels need to meet specific fuel-property requirements, a chemistry-agnostic approach to assessing the potential benefits of candidate fuels was developed using the Central Fuel Property Hypothesis (CFPH). The CFPH states that fuel properties are predictive of the performance of the fuel, regardless of the fuel's chemical composition. In order to use this hypothesis to assess the potential of fuel candidates to increase efficiency in spark-ignition (SI) engines, the individual contributions towards efficiency potential in an optimized engine must be quantified in a way that allows the individual fuel properties to be traded off for one another. This review article begins by providing an overview of the historical linkages between fuel properties and engine efficiency, including the two dominant pathways currently being used by vehicle manufacturers to reduce fuel consumption. Then, a thermodynamic-based assessment to quantify how six individual fuel properties can affect efficiency in SI engines is performed: research octane number, octane sensitivity, latent heat of vaporization, laminar flame speed, particulate matter index, and catalyst light-off temperature. The relative effects of each of these fuel properties is combined into a unified merit function that is capable of assessing the fuel property-based efficiency potential of fuels with conventional and unconventional compositions.

42 ENGINEERING↗
DOE OSTI2020

Synthesis and structural characterization of bis (2-pyridylthio)( p -tolylthio)methyl zinc complexes and the catalytic hydrosilylation of CO 2

Bis(2-pyridylthio)(p-tolylthio)methane, [Bptm STol ]H, has been synthesized by treatment of a 2:1 mixture of 2-mercaptopyridine and p-thiocresol with NaH, followed by addition of CHI3. Access to zinc complexes is provided by the reaction of [Bptm STol ]H with Zn[N(SiMe 3 ) 2 ] 2 to afford [Bptm STol ]ZnN(SiMe 3 ) 2 , from which the halide derivatives [Bptm STol ]ZnX (X = Cl, Br, I) are obtained via reaction with Me 3 SiX (X = Cl, Br, I), and the formate complex, [Bptm STol ]ZnO 2 CH, is obtained by treatment with CO 2 in the presence of PhSiH 3 . Here, the molecular structures of [Bptm STol ]ZnN(SiMe 3 ) 2 , [Bptm STol ]ZnX (X = Cl, Br, I) and [Bptm STol ]ZnO 2 CH have been determined by single crystal X-ray diffraction, which indicate that the four coordinate zinc centers adopt structures that are intermediate between idealized trigonal monopyramidal and seesaw geometries. [Bptm STol ]ZnO 2 CH is a catalyst for the hydrosilylation of CO 2 by (RO) 3 SiH at room temperature to afford the silyl formate, HCO 2 Si(OR) 3 .

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

Ammonia Synthesis by a Supported Iron-Lithium Hydride Precatalyst: Silicon Nitride Support Enabled Synthesis and Nitrogen Reservoir Dynamics

Amorphous silicon nitride (Si 3 N 4 ) is an unconventional support for the chemisorption of organometallic complexes and offers potential improvements in active site stability and reactivity through enhanced metal-nitrogen covalency and orbital overlap in bonding interactions with the nitride framework. Here, we show that silicon nitride-supported iron mesityl complexes display divergent reactivity compared to their silica-supported homologues, resisting metallic particle formation under reducing pretreatment conditions (exposure to excess organolithium reagents) and maintaining active iron/lithium speciation under ammonia synthesis conditions that is absent on the oxide support. When the organometallic iron complex on silicon nitride is exposed to excess n-butyllithium, iron remains isolated, catalyzing the conversion of butyllithium to lithium hydride, resulting in a divalent iron site in a polyhydride environment. In contrast, the silica-supported complex is converted to reduced iron clusters without forming persistent isolated hydrides. These structural differences lead to markedly different catalytic behaviors under ammonia synthesis conditions. The Li/Fe/Si 3 N 4 catalyst is highly active (7.5 mol NH 3 /mol Fe/h at 300 °C, 10 bar, or 46 mol NH 3 /mol Fe/h at 400 °C, 10 bar), while both the silica-supported analog and the nonlithiated Si 3 N 4 -supported species are inactive. Notably, this activity is enhanced relative to previously reported iron-lithium hydride composite catalysts (0.43–4.1 mol NH 3 /mol Fe/h at 300 °C, 10 bar) and relative to the industrial benchmark promoted iron catalyst KM1 (3.0 mol NH 3 /mol Fe/h at 400 °C, 10 bar). The catalyst activation and LiH/LiNH x nitrogen reservoir dynamics for Li/Fe/Si 3 N 4 are studied by X-ray Absorption, Mössbauer, and in situ DRIFT spectroscopies and isotopic exchange kinetics.

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

Gauging aromatic conjugation and charge delocalization in the aryl silanes Ph n SiH 4– n ( n = 0–4), with silicon K-edge XAS and TDDFT

In this work, Si K-edge X-ray absorption spectra (XAS) have been measured experimentally and calculated using time-dependent density functional theory (TDDFT) to investigate electronic structure in aryl silanes, PhnSiH 4– n ( n = 0–4). Adding aryl groups to SiH 4 splits the Si–H σ-antibonding orbitals into new orbitals with Si–Ph π-bonding (π b ) and π-antibonding (π*) character. Greater aryl substitution is reflected by increasingly intense Si 1s → πb and Si 1s → π* transitions, and weaker transitions into the Si–H and Si–C σ* orbitals. These observations are consistent with known trends in the hydride donor ability of aryl silanes, which is driven in part by the composition of the LUMOs and the accessibility of pathways for electron delocalization through aromatic conjugation. Methodology developed for liquid-phase Si K-edge XAS measurements on PhSiH 3 and Ph 2 SiH 2 will enable dynamic studies of chemical transformations involving siliconcontaining catalysts, intermediates, and substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Atomic Layer Deposition of Cu Electrocatalysts on Gas Diffusion Electrodes for CO 2 Reduction

Electrochemical reduction of CO 2 using Cu catalysts enables the synthesis of C 2+ products including C 2 H 4 and C 2 H 5 OH. Here, in this study, Cu catalysts were fabricated using plasma-enhanced atomic layer deposition (PEALD), achieving conformal deposition of catalysts throughout 3-D gas diffusion electrode (GDE) substrates while maintaining tunable control of Cu nanoparticle size and areal loading. The electrochemical CO 2 reduction at the Cu surface yielded a total Faradaic efficiency (FE) > 75% for C 2+ products. Parasitic hydrogen evolution was minimized to a FE of ~10%, and a selectivity of 42.2% FE for C 2 H 4 was demonstrated. Compared to a line-of-sight physical vapor deposition method, PEALD Cu catalysts show significant suppression of C 1 products compared to C 2+ , which is associated with improved control of catalyst morphology and conformality within the porous GDE substrate. Finally, PEALD Cu catalysts demonstrated a stable performance for 15 h with minimal reduction in the C 2 H 4 production rate.

42 ENGINEERING↗
DOE OSTI2026

Regioselective Hydrosilylation Catalysis with Supported Well-Defined Pt(0) Complexes: Effects of Surface Anions and Phosphenium Ligands

Achieving stable, selective single-atom catalysts is challenging because localsurface-site structures are difficult to control. Surface organometallic chemistry and organic−inorganic hybrid materials offer partial solutions, but applications to supporting zero-valent metals are limited. We demonstrate that well-defined, ionically bound N-heterocyclic phosphenium ([NHP] + ) ligands can be generated on silylium-functionalized sulfated zirconia ([ i Pr 3 Si][SZO]). These surface-bound [NHP][SZO] ligands coordinate Pt(0) centers, forming [(NHP)Pt(0)L][SZO] precatalysts that are highly active for alkyne hydrosilylation. Systematic studies reveal that sterically bulky aromatic ligands enhance regioselectivity, achieving performances comparable to molecular Pt catalysts. Further, more-coordinating anions support more-regioselective precatalysts; therefore, SZO supports more-selective species than weaker-coordinating Al(OC(CF 3 ) 3 ) 3 - functionalized silica, a trend confirmed by molecular analogues. These results demonstrate that both the ligand and support control catalytic behavior and enable solid-state structure− activity relationships.

Catalysts↗
DOE OSTI2025

Active Site Dynamics in Molybdenum-Based Silica-Supported Olefin Metathesis Catalysts: Site Renewal and Decay Beyond the Chauvin Cycle

Heterogeneous olefin metathesis catalysts exhibit low active site densities and unpredictable kinetics due to dynamic active site formation and decay processes. Here, in this study, we establish a quantitative framework that captures active site generation, renewal, and decay in olefin metathesis over silica-supported molybdenum oxide catalysts, enabling a mechanistic explanation of catalytic behavior and strategies to achieve high, stable activity. Steady-state active site titrations reveal that 2,3-dimethyl-butene isomers (4MEs) cofeeding increases active site density by up to 4.3-fold, directly correlating with enhanced metathesis rates. Spectroscopic studies demonstrate that 4MEs facilitate Mo(VI) reduction to Mo(IV) and interact strongly with surface Si–OH groups, generating labile protons that promote active site formation via a 1,2-proton shift mechanism. Kinetic modeling indicates that ethylene acts as a decay promoter, shifting kinetic control away from the Chauvin cycle and suppressing metathesis activity. Comparative studies on catalysts with varying Mo loading reveal that promotion is most effective for dispersed molybdate species, with a decline at higher Mo loadings. These findings provide a unified mechanistic framework for heterogeneous olefin metathesis, offering new strategies to enhance active site accessibility, mitigate deactivation, and optimize catalyst design.

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

Li2O-Based Cathode Additives Enabling Prelithiation of Si Anodes

Low first-cycle Coulombic efficiency is especially poor for silicon (Si)-based anodes due to the high surface area of the Si-active material and extensive electrolyte decomposition during the initial cycles forming the solid electrolyte interphase (SEI). Therefore, developing successful prelithiation methods will greatly benefit the development of lithium-ion batteries (LiBs) utilizing Si anodes. In pursuit of this goal, in this study, lithium oxide (Li2O) was added to a LiNi0.6Mn0.2Co0.2O2 (NMC622) cathode using a scalable ball-milling approach to compensate for the initial Li loss at the anode. Different milling conditions were tested to evaluate the impact of particle morphology on the additive performance. In addition, Co3O4, a well-known oxygen evolution reaction catalyst, was introduced to facilitate the activation of Li2O. The Li2O + Co3O4 additives successfully delivered an additional capacity of 1116 mAh/gLi2O when charged up to 4.3 V in half cells and 1035 mAh/gLi2O when charged up to 4.1 V in full cells using Si anodes.

25 ENERGY STORAGE↗
DOE OSTI2024

High-throughput dataset of impurity adsorption on common catalysts in biomass upgrading applications

Abstract An extensive dataset consisting of adsorption energies of pernicious impurities present in biomass upgrading processes on common catalysts and support materials has been generated. This work aims to inform catalyst and process development for the conversion of biomass-derived feedstocks to fuels and chemicals. A high-throughput workflow was developed to execute density functional theory calculations for a diverse set of atomic (Al, B, Ca, Cl, Fe, K, Mg, Mn, N, Na, P, S, Si, Zn) and molecular (COS, H 2 S, HCl, HCN, K 2 O, KCl, NH 3 ) species on 35 unique surfaces for transition-metal (Ag, Au, Co, Cu, Fe, Ir, Ni, Pd, Pt, Re, Rh, Ru) and metal-oxide (Al 2 O 3 , MgO, anatase-TiO 2 , rutile-TiO 2 , ZnO, ZrO 2 ) catalysts and supports. Approximately 3,000 unique adsorption geometries and corresponding adsorption energies were obtained.

09 BIOMASS FUELS↗