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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Morphological Tuning of Nanoporous Metals Prepared with Conversion Reaction Synthesis via Thermal Annealing

We report that conversion reaction synthesis, namely, reacting an organolithium reducing agent with a metal chloride to produce a metal/LiCl nanocomposite and then removing lithium chloride with a polar organic solvent, is an efficient and scalable way to fabricate a variety of three-dimensional, bicontinuous nanoporous transition metals. Thermal annealing was investigated as a means to tune the morphology of these nanoporous metals. X-ray diffraction studies were used to investigate the effect of thermal annealing on the size and strain of phases in Cu/ LiCl, Co/LiCl, and Fe/LiCl nanocomposites, while electron microscopy and nitrogen adsorption studies were used to study the porosity and surface properties of the resulting nanoporous metals after LiCl was removed from the annealed nanocomposites. Annealing metal/LiCl nanocomposites resulted in the controlled growth of the metal nanoparticles, the rate of which depended on the diffusivity of the metal. It was observed that annealing nanocomposites produced more robust nanoporous metals with increased porosity under certain conditions. In conclusion, it was found that annealing the as-formed nanocomposites rather than the isolated nanoporous metals provides finer control of the conversion synthesis process and allows for the design of more optimized pore structures and thus enhanced suitability for catalytic and electrochemical applications.

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

Hydrophobic Nanoconfinement Enhances CO 2 Conversion to H 2 CO 3

Understanding the formation of H 2 CO 3 in water from CO 2 is important in environmental and industrial processes. Although numerous investigations have studied this reaction, the conversion of CO 2 to H 2 CO 3 in nanopores, and how it differs from that in bulk water, has not been understood. We use ReaxFF metadynamics molecular simulations to demonstrate striking differences in the free energy of CO 2 conversion to H 2 CO 3 in bulk and nanoconfined aqueous environments. We find that nanoconfinement not only reduces the energy barrier but also reverses the reaction from endothermic in bulk water to exothermic in nanoconfined water. Also, charged intermediates are observed more often under nanoconfinement than in bulk water. Stronger solvation and more favorable proton transfer with increasing nanoconfinement enhance the thermodynamics and kinetics of the reaction. Here our results provide a detailed mechanistic understanding of an important step in the carbonation process, which depends intricately on confinement, surface chemistry, and CO 2 concentration.

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

Photochemical Au(I)–Au(I) Bond Formation: A Battle between Intersystem Crossing and Internal Conversion

The transition metal complex Au(CN) 2 – has provided experimental evidence of photoinduced bond formation between Au(I) atoms in solution. However, the underlying photochemical driving force for this bond formation reaction remains unclear. In this study, we investigate the ultrafast Au–Au bonding process in the [Au(CN) 2 ] 2 2– dimer using nonadiabatic dynamics simulations that incorporate intersystem crossing and internal conversion pathways. Reaction pathways and transitions among photochemically accessible singlet and triplet excited states are analyzed. Computational results indicate that intersystem crossing is the primary driving force in the early stages of ultrafast photochemical dynamics, while internal conversion among triplet states plays a critical role after the system stabilizes in a higher-lying triplet state. Furthermore, this work provides a mechanistic perspective on modulating photochemical reactions by tuning the relative strengths of spin–orbit coupling and nonadiabatic coupling.

Computational chemistry↗
DOE OSTI2019

Synergistic Effect of Chlorination and Selenophene: Achieving Elevated Solar Conversion in Highly Aggregated Systems

Chlorination and selenophene were used to develop benzothiadiazole-based polymers for high-performance polymer solar cells (PSCs). The introduction of selenophene can increase crystallinity due to the metalloid nature of selenium and thus facilitate charge transport. Chlorination can tune the energy levels and induce strong aggregation due to its unique features. A non-chlorinated polymer with selenophene, PBT3TSe, shows a highly crystalline structure and a dominant face-on orientation, consequently attaining a high short-circuit current (J(SC)). Chlorinated PBT3TClSe displays synergy between the advantages of chlorination and selenophene to achieve elevated photovoltaic performance, with a power conversion efficiency (PCE) approaching 9.89% in PC 71 BM-based devices. Interestingly, chlorination has an important influence on morphology of the polymer and polymer blend films, resulting in a severe aggregation and mixed face-on and edge-on orientation in the blend film. But the sufficient intermingling of donor and acceptor and the closer distances between molecules from the introduction of the chlorine and selenophene offset their morphological inferiority to achieve higher solar conversion.

14 SOLAR ENERGY↗
DOE OSTI2023

Co 2 Mo 6 S 8 Catalyzes Nearly Exclusive Electrochemical Nitrate Conversion to Ammonia with Enzyme-like Activity

Electrocatalytic nitrate to ammonia conversion is a key reaction for energy and environmental sustainability. This reaction involves complex multi electron and proton transfer steps, and is impeded by the lack of catalyst for promoting both reactivity and ammonia selectivity. Here, we demonstrate active motifs based on the Chevrel phase Co 2 Mo 6 S 8 exhibit an enzyme-like high turnover frequency of ~95.1 s –1 for nitrate electroreduction to ammonia. We reveal strong synergy of multiple binding sites on this catalyst, such that the ligand effect of Co steers H ad* toward hydrogenation other than hydrogen evolution, the ensemble effect of Co, and the spatial confinement effect that promote the full hydrogenation of NO x to ammonia without N–N coupling. The catalyst exhibits almost exclusive ammonia conversion with a Faradaic efficiency of 97.1% and ammonia yielding rate of 115.5 mmol·g cat –1 ·h –1 in neutral electrolytes. The high activity was also confirmed in electrolytes with dilute nitrate and high chloride concentrations.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Forum on Materials and Interfaces for Energy Storage and Conversion

This ACS Applied Materials & Interfaces forum on energy storage and conversion contains the topics of research discoveries to advance energy technology development. The topics are focused on the efficient and sustainable use of energy in the fields of fuel cells, CO 2 conversion, water splitting, batteries, and electrochemical capacitor. This forum highlights recent achievements in these emerging technologies through the design and evaluation of novel materials and devices and theoretical study. Additionally, this forum also showcases the technology at all stages of development from “embryonic” conception to industrial adaptation.

25 ENERGY STORAGE↗
DOE OSTI2020

Tribochemical Conversion of Methane to Graphene and Other Carbon Nanostructures: Implications for Friction and Wear

Tribochemistry involves chemical reactions occurring at sliding contact interfaces in the presence of gaseous and/or liquid media. It often leads to the formation of a solid reaction film (also termed boundary film) which controls friction and wear and hence the efficiency and reliability of moving mechanical systems (such as engines). Here we demonstrate tribochemical conversion of methane to graphene, nano-onion, and disordered carbons on the sliding surfaces of Ni-, Cu-, and CuNi-containing VN coatings at atmospheric pressure and room temperature, providing 2-3 orders of magnitude reduction in wear and similar to 50% reduction in friction compared to those of the uncoated steels. Transmission electron microscopy confirms that graphene forms preferably on metal rich nanoclusters of the composite coatings, while the carbon nano-onions are scattered throughout the carbon tribofilm. Ab initio molecular dynamics simulations elucidate underlying mechanisms involved in the tribochemical conversion of methane to carbon- based nanostructures in support of microscopic observations. These scientific findings may lead to new materials technologies that can use methane as a source for continuous and in situ lubrication. For example, there is an urgent need to curtail the uses of lubricating oils in natural gas compressors and engines as they contaminate the natural gas being compressed or burnt.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Microwave-Assisted Synthesis of Cu@IrO 2 Core-Shell Nanowires for Low-Temperature Methane Conversion

A facile microwave-assisted synthesis was developed for the tunable fabrication of a novel Cu@IrO 2 core@shell nanowire motif. Experimental parameters, such as (i) reaction time, (ii) the method of addition of the Ir precursor, (iii) capping agent, (iv) reducing agent, as well as (v) the capping agent-to-reducing agent ratio, were subsequently optimized. The viability of other methods based on previously reported literature, such as refluxing, stirring, and physical sonication, was studied and compared with our optimized microwave-assisted protocol in creating our as-prepared materials. It should be noted that the magnitude of the IrO 2 shell could be tailored based on varying the Cu: Ir ratio coupled with judicious variations in the amounts of capping agent and reducing agent. Structural characterization techniques, such as XRD, XPS, and HRTEM (including HRTEM-EDS), were used to analyze our Cu@IrO 2 motifs. Specifically, the shell could be reliably tailored from sizes of 10 nm, 8 nm, 6 nm, and 3.5 nm with corresponding Cu: Ir ratios of 10:1, 15:1, 20:1, and 25:1, respectively. Moreover, the structural integrity of the motifs was probed and found to have been maintained after not only heat treatment but also the post-methane conversion process, indicative of an intrinsically high stability. Both components within the CuO-IrO 2 interface were able to activate methane at temperatures between 400 to 500 K with a reduction of the associated metal cations (Cu 2+ → Cu 1+ ; Ir 4+ → Ir 3+ ) and the deposition of CH x fragments on the surface, as clearly observed in the ambient-pressure XPS results. Thus, on the basis of their stability and chemical activity, these core-shell materials could be very useful for the catalytic conversion of methane into 'higher value" chemicals.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Structure and Magnetism Evolution from FeCo Nanoparticles to Hollow Nanostructure Conversion for Magnetic Applications

Hollow nanostructures have witnessed an increasing interest in emerging fields, including energy storage electrodes, nanocatalysis, photonics, and biomedical carriers, etc. The fundamental mechanisms for hollowing conversion chemistry of complex nanoalloys is indispensable to grow such nanostructures with controlled compositions and functionalities. In this contribution, the Kirkendall effect on magnetic Fe-Co bimetallic alloys with the formation of hollow nanostructures for exchange interactions was studied. The rich diffusion kinetics of binary Fe-Co alloys accompanied with its conversion from solid, core-shell to hollow nanostructures were been captured through X-ray spectroscopy and electron microscopy. We further report the cation exchange improved magnetic performance of hollow nanostructures with increasing the crystallinity.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Ethanol Conversion over La 0.7 Sr 0.3 MnO 3–x (100): Autocatalysis, Adjacent O-Vacancies, Disproportionation, and Dehydrogenation

The mechanism for catalytic conversion of ethanol over La 0.7 Sr 0.3 MnO 3– x (100) surface to acetaldehyde and ethene was investigated. Pre-exposure temperature-programmed reaction (PE-TPR) experiments were performed in which ethanol was introduced to oxidized or reduced surfaces followed by heating. In particular, sequential PE-TPR experiments were conducted to incrementally and gradually reduce the surface. The products and their ratios were investigated as a function of surface reduction. The data show that acetaldehyde and ethene production is catalyzed with hydrogen abstraction and oxygen abstraction reactions occurring by intermediates in vacancies at various temperatures >400 K. Adsorption of acetaldehyde followed by a temperature-programmed reaction does not produce ethene, indicating that acetaldehyde is not an intermediate to ethene and that the hydrogen and oxygen abstraction from ethanol to ethene are decoupled steps. Further evidence for this mechanistic nuance was obtained using isotopically labeled ethanol (CD 3 CH 2 OH), which produces CD 3 CHO and CD 2 CH 2 . Additionally, the ratio of aldehyde production to alkene production increases with reduction, suggesting that aldehyde is produced from a disproportionation reaction between ethoxy species in adjacent O-vacancies, while ethene is produced from a dehydrogenation reaction with ethoxy species in vacancies without requiring adjacent O-vacancies. Counterintuitively, this finding indicates that the more oxygenated product (aldehyde vs ethene) is favored with more vacancies and that the net alcohol conversion is autocatalytic. Density functional theory calculations were able to find the previously unknown disproportionation pathway between ethoxies in adjacent O-vacancies, and kinetic Monte Carlo simulations support this interpretation by reproducing experimental selectivities. The activation energies for these pathways are estimated as 132 ± 10 kJ/mol for the disproportionation reaction (when occurring between ethoxies in adjacent vacancies) and as 148 ± 11 kJ/mol for the direct dehydrogenation reaction of an ethoxy in a vacancy. Based on these results, a mechanism with operative pathways based on elementary steps in O-vacancies is reported.

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

Electrochemically Engineered, Highly Energy-Efficient Conversion of Ethane to Ethylene and Hydrogen below 550 °C in a Protonic Ceramic Electrochemical Cell

Ethylene is one of the largest building blocks in the petrochemical industry, mainly produced by steam cracking of ethane derived from naphtha or shale gas at high temperatures (>800 °C). Despite its technical maturity and economic competitiveness, the thermal steam cracking of ethane is highly energy-intensive. In this work, an electrochemically engineered direct conversion process of ethane to produce hydrogen and ethylene using a planar protonic ceramic membrane reactor with a bi-functional three-dimensional catalytic electrode is reported, with a single-pass ethane conversion of 40% and ethylene yield of 26.7% at 550 °C. Compared with the industrial ethane steam cracking, this method saves process energy input by 45.1% and improves process energy efficiency by 50.6%, based on comprehensive process simulation using Aspen Plus software. Further, steam electrolysis treatment under the solid oxide electrolysis cell mode can regenerate the system’s catalytic performance and significantly alleviate catalytic degradation by 74%, demonstrating high techno-economic viability.

bi-functional electrode↗
DOE OSTI2023

A Bifunctional Ionic Liquid for Capture and Electrochemical Conversion of CO 2 to CO over Silver

Electrochemical conversion of CO 2 requires selective catalysts and high solubility of CO 2 in the electrolyte to reduce the energy requirement and increase the current efficiency. In this study, the CO 2 reduction reaction (CO 2 RR) over Ag electrodes in acetonitrile-based electrolytes containing 0.1 M [EMIM][2-CNpyr] (1-ethyl-3-methylimidazolium 2-cyanopyrolide), a reactive ionic liquid (IL), is shown to selectively (>94%) convert CO 2 to CO with a stable current density (6 mA·cm –2 ) for at least 12 h. The linear sweep voltammetry experiments show the onset potential of CO 2 reduction in acetonitrile shifts positively by 240 mV when [EMIM][2-CNpyr] is added. This is attributed to the pre-activation of CO 2 through the carboxylate formation via the carbene intermediate of the [EMIM] + cation and the carbamate formation via binding to the nucleophilic [2-CNpyr] – anion. The analysis of the electrode–electrolyte interface by surface-enhanced Raman spectroscopy (SERS) confirms the catalytic role of the functionalized IL where the accumulation of the IL-CO 2 adduct between –1.7 and –2.3 V vs Ag/Ag + and the simultaneous CO formation are captured. Furthermore, this study reveals the electrode surface species and the role of the functionalized ions in lowering the energy requirement of CO 2 RR for the design of multifunctional electrolytes for the integrated capture and conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Dynamic Activation of Single-Atom Catalysts by Reaction Intermediates: Conversion of Formic Acid on Rh/Fe 3 O 4 (001)

The stability and activity of supported single-atom catalysts (SACs) represent critical yet opposing factors limiting our ability to explore and exploit their unique properties. Here, this study demonstrates the operation of a switchable catalyst that is activated in the presence of surface intermediates and reverts back to a stable but inactive form when the reaction is completed. We employ atomically defined Rh-Fe 3 O 4 (001) catalysts to demonstrate how structurally stable Rh, bound in surface octahedral Fe sites, gets destabilized to form highly active Rh adatoms and small clusters. Conversion of formic acid, leading initially to surface formate and hydroxyl species, is employed as a model reaction to probe the dynamics of such processes. We find that surface hydroxyl recombination to water through the Mars van Krevelen mechanism reduces Rh coordination, triggering its conversion to active Rh adatoms. Since such lattice oxygen exchange is observed in many acid-base and redox chemistries, the process can be broadly applicable to controlling the activation of the range of SACs.

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

Discovering Ni/Cu Single-Atom Alloy as a Highly Active and Selective Catalyst for Direct Methane Conversion to Ethylene: A First-Principles Kinetic Study

Direct methane conversion to liquid fuels or value-added chemicals is a promising technology to utilize natural resources without resorting to further petroleum extraction. However, discovering efficient catalysts for this reaction is challenging due to either coke formation or unfavorable C-H bond activation. Herein, we design single-atom alloy (SAA) catalysts to simultaneously eliminate the above two bottlenecks based on mechanism-guided strategies: (1) the active single atom enables favorable C-H bond breaking and (2) the less reactive host metal facilitates C-C coupling and thus avoids strong binding of carbonaceous species. Employing electronic structure theory calculations, we screened the stability of multiple SAAs with 3d-5d transition metals atomically dispersed on a copper surface in terms of avoiding dopant aggregation and segregation. We then evaluated reactivities of the stable SAAs as catalysts for direct methane conversion to C2 products, including methane dehydrogenation and C-C coupling mechanisms. Combining selectivity analysis with kinetic modeling, we predicted that nickel dispersed on copper, i.e., Ni/Cu SAA, is a highly active and selective catalyst that can efficiently transform methane to ethylene. This work designs efficient SAA catalysts for direct methane activation and provides chemical insights into engineering compositions of SAAs to tune their catalytic performances.

Kothakonda, Manish↗
DOE OSTI2017

Density Functional Theory (DFT) Study To Unravel the Catalytic Properties of M-Exchanged MFI, (M = Be, Co, Cu, Mg, Mn, Zn) for the Conversion of Methane and Carbon Dioxide to Acetic Acid

The conversion of greenhouse gases, such as CO 2 and CH 4 , to value chemicals is a major challenge, because of the high stability of both molecules. In this study, density functional theory (DFT) calculations with long-range corrections and ONIOM were used to analyze the reaction mechanism for the conversion of CO 2 and CH 4 to acetic acid with MFI zeolite exchanged with Be, Co, Cu, Mg, Mn, and Zn cations. Our results demonstrate that (a) the highest reaction barrier on the reaction mechanism is CH 4 dissociation, and the transition state energy in that step is directly related to the energy of the lowest unoccupied molecular orbital and the electronegativity of the metal exchanged zeolites; (b) a charge transfer between CH 4 and the metal cation occurs simultaneously to CH 4 dissociation; (c) CO 2 insertion has a low energy barrier, and the protonation of the acetate species is spontaneous; (d) dispersion interactions are the main contributions to CH 4 adsorption energies, whereas, in the rest of the steps of the reaction mechanism, the contribution of dispersion to the energies of reaction is almost negligible; (e) desorption of acetic acid could be promoted by the coadsorption of water; and (f) CH 4 dissociation on Cu-MFI has an apparent activation energy of 11.5 kcal/mol, and a forward rate constant of 1.1 s–1 at 398 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Insight into the Selectivity of Isopropanol Conversion at Strontium Titanate (100) Surfaces: A Combination Kinetic and Spectroscopic Study

This work aims to better understand the role of interfacial molecular structure that governs selectivity and activity in heterogeneous catalytic reactions. To address this, a comprehensive study of isopropanol conversion over an archetypal perovskite material, strontium titanate (SrTiO 3 or STO), was performed with an array of techniques sensitive to orthogonal aspects of the ensuing chemistry. Cubic-shape STO nanoparticles with only the (100) facet exposed were synthesized and used to study the ensemble kinetic conversion of isopropanol over the surfaces, which showed a remarkable selectivity to form acetone, with minor propylene products appearing at elevated temperatures. These results in combination with inelastic neutron scattering measurements provide not only new insight into the selectivity and overall activity of the catalysts but also low frequency vibrational signatures of the adsorbed and reacted species. To compliment these measurements, pristine thin films of STO (100) were synthesized and used in combination with vibrational sum frequency generation spectroscopy to extract the absolute molecular orientation of the adsorbed molecules at the interface. It was found that the isopropanol assumes an orientation where the -CH group points towards the STO surface; this pre-reaction geometry offers an obvious pathway to produce acetone by abstracting the alpha-proton and, thus, provides a mechanistic explanation of selectivity at STO (100) surfaces. This new insight opens up pathways to explore and modify surfaces to tune the activity/selectivity though a molecular level understanding of the reactions at the surface.

36 MATERIALS SCIENCE↗
DOE OSTI2026

NH 3 -Mediated Reactive Capture and Conversion: Integrating CO 2 Absorption from Flue Gas with CO Production via NH 4 HCO 3 Electrolysis

Efficient carbon capture and utilization require strategies that minimize energy penalties of CO 2 regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO 2 from simulated flue gas (10% v/v CO 2 in N 2 ) with electroreduction of NH 4 HCO 3 to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO 2 capture with C/N ratio of 0.65 was achieved using 2.5 M NH 3 from simulated flue gas. Electrolysis of the resulting NH 4 HCO 3 on the Ni- SAC delivered an 85% CO Faradaic efficiency at 100 mA/cm 2 with excellent tolerance to NH 3 /NH 4 + as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2017

Controlling Solid–Liquid Conversion Reactions for a Highly Reversible Aqueous Zinc–Iodine Battery

Aqueous rechargeable batteries are desirable for many energy storage applications due to their low cost and high safety. However, low capacity and short cycle life are the significant obstacles to their practical applications. Here, we demonstrate a highly reversible aqueous zinc-iodine battery using encapsulated iodine in microporous active carbon fibers (ACFs) as cathode materials through the rational control of solid-liquid conversion reactions. The experiments and density function theory (DFT) calculations were employed to investigate the effects of solvents and properties of carbon hosts, e.g. pore size, surface chemistries, on the adsorption of iodine species. The rational manipulation of the competition between the adsorption in carbon and solvation in electrolytes for iodine species is responsible for the high reversibility and cycling stability. The zinc-iodine batteries deliver a high capacity of 180 mAh g-1 at 1C and a stable cycle life over 3000 cycles with ~90% capacity retention as well as negligible self-discharge. We believe the principles for stabilizing the zinc-iodine system could provide new insight into conversion systems such as Li-S systems.

Environmental Molecular Sciences Laboratory↗