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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 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Modulating CO 2 Electrocatalytic Conversion to the Organics Pathway by the Catalytic Site Dimension

Electrochemical reduction of carbon dioxide to organic chemicals provides a value-added route for mitigating greenhouse gas emissions. Here, we report a family of carbon-supported Sn electrocatalysts with the tin size varying from single atom, ultrasmall clusters to nanocrystallites. High single-product Faradaic efficiency (FE) and low onset potential of CO 2 conversion to acetate (FE = 90% @ –0.6 V), ethanol (FE = 92% @ –0.4 V), and formate (FE = 91% @ –0.6 V) were achieved over the catalysts of different active site dimensions. The CO 2 conversion mechanism behind these highly selective, size-modulated p-block element catalysts was elucidated by structural characterization and computational modeling, together with kinetic isotope effect investigation.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Integrated CO 2 Capture and Conversion by a Robust Cu(I)-Based Metal–Organic Framework

Metal-organic frameworks (MOFs) have shown promise in both capturing CO 2 under flue gas conditions and converting it into valuable chemicals. However, the development of a single MOF capable of capturing and selectively converting CO 2 has remained elusive due to lack of harmonious combination of selectivity, water stability, and reactivity. For example, Cu(I)-based MOFs are particularly effective for CO 2 conversion, but they do not typically exhibit selective CO 2 adsorption and often suffer from instability in the presence of air and moisture. Developing a Cu(I) MOF that is stable under flue gas conditions while also capturing CO 2 from this mixture would likely afford a material capable of selectively capturing and converting CO 2 in an integrated pathway, which would represent a significant advancement in this field. In this study, we introduce NU-2100, an ultramicroporous Cu(I) MOF, which exhibits both selectivity for CO 2 adsorption and great stability even in the presence of moisture and air. Comprehensive evaluations involving exposure to air, oxygen, water, and varying temperatures reveal that NU-2100 demonstrates superior stability compared to other known Cu(I) MOFs. Utilizing adsorption isotherms and thermogravimetric analysis coupled with gas chromatography-mass spectrometry (TGA-GCMS), we establish the high selectivity of NU-2100 for CO 2 over common flue gas components, including water, nitrogen, and oxygen. Additionally, under mild reaction conditions (50 °C and H 2 :CO 2 = 3:1), NU-2100 exhibits CO 2 capture and catalytic conversion to formic acid with 100% selectivity. Furthermore, this study marks an important step towards the design of next-generation MOFs capable of integrated carbon capture and utilization (iCCU) under industrial conditions.

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

Porous and Amorphous Mn x Mo 3 S 13 Chalcogel Electrode for High-Capacity Conversion-Based Lithium-Ion Batteries

While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, in this study, we present a porous, amorphous, sulfide-based Mn x Mo 3 S 13 chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn x Mo 3 S 13 (x = 0.25) chalcogel exhibits a local structure that resembles the Mo 3 S 13 cluster with Mn 2+ distributed across the Mo 3 S 13 matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn 2+ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo 3 S 13 chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn 0.25 Mo 3 S 13 half-cell delivers 897 mAh g –1 capacity during the first discharge and retains 571 mAh g –1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo 3 S 13 cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn 0.25 Mo 3 S 13 structure and the strong affinity of Lewis-acidic Mn 2+ for polysulfide anions generated during the charge–discharge process of the Li/Mn 0.25 Mo 3 S 13 cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.

25 ENERGY STORAGE↗
DOE OSTI2015

Carbon Dioxide Conversion to Methanol over Size-Selected Cu 4 Clusters at Low Pressures

In order to utilize the captured CO 2 , the activation of CO 2 and its hydrogenation to methanol are of much interest . We investigate the use of size-selected Cu-4 clusters supported on Al 2 O 3 thin films for CO 2 reduction in the presence of hydrogen. The catalytic activity was measured under near-atmospheric reaction conditions with a low CO 2 partial pressure, and the oxidation state of the clusters was investigated by in situ grazing incidence X-ray absorption spectroscopy. The results indicate that size-selected Cu-4 clusters are the most active low-pressure catalyst for catalytic CO 2 conversion to CH 3 OH. Density functional theory calculations reveal that Cu-4 clusters have a low activation barrier for conversion of CO 2 to CH 3 OH. Our study suggests that small Cu clusters may be excellent and efficient catalysts for the recycling of released CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Highly active Au/δ-MoC and Cu/δ-MoC catalysts for the conversion of CO 2 : The metal/C ratio as a key factor defining activity, selectivity, and stability

The ever growing increase of CO 2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO 2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO 2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo 2 C and Au/δ-MoC catalysts provides evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO 2 conversion. Here, a control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Plasmon-Enhanced Photocatalytic CO 2 Conversion within Metal–Organic Frameworks under Visible Light

Materials development for artificial photosynthesis, in particular, CO 2 reduction, has been under extensive efforts, ranging from inorganic semiconductors to molecular complexes. In this report, we demonstrate a metal-organic framework (MOF)-coated nanoparticle photocatalyst with enhanced CO 2 reduction activity and stability, which stems from having two different functional units for activity enhancement and catalytic stability combined together as a single construct. Covalently attaching a CO 2 -to-CO conversion photocatalyst Re I (CO) 3 (BPYDC)Cl, BPYDC = 2,2'-bipyridine-5,5'-dicarboxylate, to a zirconium MOF, UiO-67 (Re n -MOF), prevents dimerization leading to deactivation. By systematically controlling its density in the framework (n = 0, 1, 2, 3, 5, 11, 16, and 24 complexes per unit cell), the highest photocatalytic activity was found for Re 3 -MOF. Structural analysis of Re n -MOFs suggests that a fine balance of proximity between photoactive centers is needed for cooperatively enhanced photocatalytic activity, where an optimum number of Re complexes per unit cell should reach the highest activity. Here, based on the structure-activity correlation of Re n -MOFs, Re 3 -MOF was coated onto Ag nanocubes (Ag$\subset$Re 3 -MOF), which spatially confined photoactive Re centers to the intensified near-surface electric fields at the surface of Ag nanocubes, resulting in a 7-fold enhancement of CO 2 -to-CO conversion under visible light with long-term stability maintained up to 48 h.

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

Selective Conversion of Carbon Dioxide to Formaldehyde via a Bis(silyl)acetal: Incorporation of Isotopically Labeled C 1 Moieties Derived from Carbon Dioxide into Organic Molecules

The conversion of carbon dioxide to formaldehyde is a transformation that is of considerable significance in view of the fact that formaldehyde is a widely used chemical, but this conversion is challenging because CO 2 is resistant to chemical transformations. Therefore, we report here that formaldehyde can be readily obtained from CO 2 at room temperature via the bis(silyl)acetal, H 2 C(OSiPh 3 ) 2 . Specifically, formaldehyde is released from H 2 C(OSiPh 3 ) 2 upon treatment with CsF at room temperature. H 2 C(OSiPh 3 ) 2 thus serves as a formaldehyde surrogate and provides a means to incorporate CH x (x = 1 or 2) moieties into organic molecules. Here, isotopologues of H 2 C(OSiPh 3 ) 2 may also be synthesized, thereby providing a convenient means to use CO 2 as a source of isotopic labels in organic molecules.

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

Exploring Ion Mobility Mass Spectrometry Data File Conversions to Leverage Existing Tools and Enable New Workflows

Ion mobility (IM) is often combined with LC-MS experiments to provide an additional dimension of separation for complex sample analysis. While highly complex samples are better characterized by the full dimensionality of LC-IM-MS experiments to uncover new information, downstream data analysis workflows are often not equipped to properly mine the additional IM dimension. For many samples the data acquisition benefits of including IM separations are all that is necessary to uncover sample information and the full dimensionality of the data is not required for data analysis. Post-acquisition reduction and adaptation of the dimensions of LC-IM-MS and IM-MS experiments into an LC-MS format opens the possibility to use a plethora of existing software tools. In this work, we developed data file conversion tools to reduce the complexity of IM data analysis. Three data file transformations are introduced in the PNNL PreProcessor software: 1) mapping the IM axis to the LC axis for IM-MS data, 2) converting the drift time vs. m/z space to CCS/z vs m/z space, and 3) transforming All Ions IM/MS mobility aligned fragmentation data to a standard LC-MS DDA data file format. Finally, these new data file conversions are demonstrated with corresponding lipidomics and proteomics workflows that leverage existing LC-MS data analysis software to highlight the benefits of the data transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Bifunctional non-noble metal oxide nanoparticle electrocatalysts through lithium-induced conversion for overall water splitting

Developing earth-abundant, active and stable electrocatalysts which operate in the same electrolyte for water splitting, including oxygen evolution reaction and hydrogen evolution reaction, is important for many renewable energy conversion processes. Here we demonstrate the improvement of catalytic activity when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (B20 nm) are electrochemically transformed into ultra-small diameter (2–5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. We demonstrate that lithium-induced ultra-small NiFeOx nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base. We achieve 10 mA cm 2 water-splitting current at only 1.51 V for over 200 h without degradation in a two-electrode configuration and 1 M KOH, better than the combination of iridium and platinum as benchmark catalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Reversible aqueous zinc/manganese oxide energy storage from conversion reactions

Rechargeable aqueous batteries are attracting growing interest for energy storage due to their low cost and high safety. Fundamental understanding of highly reversible aqueous reactions is critical for building high-performance batteries. Herein, we studied the reversibility of Zn/MnO2 battery chemistry in mild aqueous MnSO4 electrolytes. α-MnO2 nanofibers were used as a high performance cathode. Our study provides good evidence for a conversion reaction mechanism through reversible formation of short nanorods and nanoparticle aggregates. This reversible conversion reaction provides an operating voltage of 1.44 V, high capacity of 285 mAh g-1, excellent rate and capacity retention of 92% after 5000 cycles. Zn metal anode also shows high reversibility in the mild aqueous MnSO4 electrolytes. The highly reversible and stable chemistries in aqueous Zn/MnO2 batteries open new opportunity for energy storage technologies with potentially high energy density, high safety, and low cost.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

Direct solar-to-hydrogen conversion via inverted metamorphic multi-junction semiconductor architectures

Solar water splitting via multi-junction semiconductor photoelectrochemical cells provides direct conversion of solar energy to stored chemical energy as hydrogen bonds. Economical hydrogen production demands high conversion efficiency to reduce balance-of-systems costs. For sufficient photovoltage, water-splitting efficiency is proportional to the device photocurrent, which can be tuned by judicious selection and integration of optimal semiconductor bandgaps. Here, we demonstrate highly efficient, immersed water-splitting electrodes enabled by inverted metamorphic epitaxy and a transparent graded buffer that allows the bandgap of each junction to be independently varied. Voltage losses at the electrolyte interface are reduced by 0.55 V over traditional, uniformly p-doped photocathodes by using a buried p-n junction. Lastly, advanced on-sun benchmarking, spectrally corrected and validated with incident photon-to-current efficiency, yields over 16% solar-to-hydrogen efficiency with GaInP/GaInAs tandem absorbers, representing a 60% improvement over the classical, high-efficiency tandem III-V device.

14 SOLAR ENERGY↗
DOE OSTI2017

Stabilization of ultrathin (hydroxy)oxide films on transition metal substrates for electrochemical energy conversion

Design of cost-effective electrocatalysts with enhanced stability and activity is of paramount importance for the next generation of energy conversion systems, including fuel cells and electrolyzers. However, electrocatalytic materials generally improve one of these properties at the expense of the other. Here, using Density Functional Theory calculations and electrochemical surface science measurements, we explore atomic-level features of ultrathin (hydroxy)oxide films on transition metal substrates and demonstrate that these films exhibit both excellent stability and activity for electrocatalytic applications. The films adopt structures with stabilities that significantly exceed bulk Pourbaix limits, including stoichiometries not found in bulk and properties that are tunable by controlling voltage, film composition, and substrate identity. Using nickel (hydroxy)oxide/Pt(111) as an example, we further show how the films enhance activity for hydrogen evolution through a bifunctional effect. Finally, the results suggest design principles for a new class of electrocatalysts with simultaneously enhanced stability and activity for energy conversion.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Photon–photon chemical thermodynamics of frequency conversion processes in highly multimode systems

Abstract Frequency generation in highly multimode nonlinear optical systems is inherently a complex process, giving rise to an exceedingly convoluted landscape of evolution dynamics. While predicting and controlling the global conversion efficiencies in such nonlinear environments has long been considered impossible, here, we formally address this challenge even in scenarios involving a very large number of spatial modes. By utilizing fundamental notions from optical statistical mechanics, we develop a universal theoretical framework that effectively treats all frequency components as chemical reactants/products, capable of undergoing optical thermodynamic reactions facilitated by a variety of multi-wave mixing effects. These photon–photon reactions are governed by conservation laws that directly determine the optical temperatures and chemical potentials of the ensued chemical equilibria for each frequency species. In this context, we develop a comprehensive stoichiometric model and formally derive an expression that relates the chemical potentials to the optical stoichiometric coefficients, in a manner akin to atomic/molecular chemical reactions. This advancement unlocks new predictive capabilities that can facilitate the optimization of frequency generation in highly multimode photonic arrangements, surpassing the limitations of conventional schemes that rely exclusively on nonlinear optical dynamics. Notably, we identify a universal regime of Rayleigh–Jeans thermalization where an optical reaction at near-zero optical temperatures can promote the complete and entropically irreversible conversion of light to the fundamental mode at a target frequency. Our theoretical results are corroborated by numerical simulations in settings where second-harmonic generation, sum-frequency generation and four-wave mixing processes can manifest.

Optics↗
DOE OSTI2020

Rainforest-to-pasture conversion stimulates soil methanogenesis across the Brazilian Amazon

The Amazon rainforest is a biodiversity hotspot and large terrestrial carbon sink threatened by agricultural conversion. Rainforest-to-pasture conversion stimulates the release of methane, a potent greenhouse gas. The biotic methane cycle is driven by microorganisms; therefore, this study focused on active methane-cycling microorganisms and their functions across land-use types. We collected intact soil cores from three land use types (primary rainforest, pasture, and secondary rainforest) of two geographically distinct areas of the Brazilian Amazon (Santarém, Pará and Ariquemes, Rondônia) and performed DNA stable-isotope probing coupled with metagenomics to identify the active methanotrophs and methanogens. At both locations, we observed a significant change in the composition of the isotope-labeled methane-cycling microbial community across land use types, specifically an increase in the abundance and diversity of active methanogens in pastures. We conclude that a significant increase in the abundance and activity of methanogens in pasture soils could drive increased soil methane emissions. Furthermore, we found that secondary rainforests had decreased methanogenic activity similar to primary rainforests, and thus a potential to recover as methane sinks, making it conceivable for forest restoration to offset greenhouse gas emissions in the tropics. These findings are critical for informing land management practices and global tropical rainforest conservation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

New approach to waste-heat energy harvesting: pyroelectric energy conversion

Harvesting waste heat for useful purposes is an essential component of improving the efficiency of primary energy utilization. Today, approaches such as pyroelectric energy conversion are receiving renewed interest for their ability to turn wasted energy back into useful energy. From this perspective, the need for these approaches, the basic mechanisms and processes underlying their operation, and the material and device requirements behind pyroelectric energy conversion are reviewed, and the potential for advances in this area is also discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Discovery of ZrCoBi based half Heuslers with high thermoelectric conversion efficiency

Abstract Thermoelectric materials are capable of converting waste heat into electricity. The dimensionless figure-of-merit (ZT), as the critical measure for the material’s thermoelectric performance, plays a decisive role in the energy conversion efficiency. Half-Heusler materials, as one of the most promising candidates for thermoelectric power generation, have relatively low ZTs compared to other material systems. Here we report the discovery of p -type ZrCoBi-based half-Heuslers with a record-high ZT of ∼1.42 at 973 K and a high thermoelectric conversion efficiency of ∼9% at the temperature difference of ∼500 K. Such an outstanding thermoelectric performance originates from its unique band structure offering a high band degeneracy ( N v ) of 10 in conjunction with a low thermal conductivity benefiting from the low mean sound velocity ( v m ∼2800 m s −1 ). Our work demonstrates that ZrCoBi-based half-Heuslers are promising candidates for high-temperature thermoelectric power generation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

Wavelength conversion through plasmon-coupled surface states

Surface states generally degrade semiconductor device performance by raising the charge injection barrier height, introducing localized trap states, inducing surface leakage current, and altering the electric potential. We show that the giant built-in electric field created by the surface states can be harnessed to enable passive wavelength conversion without utilizing any nonlinear optical phenomena. Photo-excited surface plasmons are coupled to the surface states to generate an electron gas, which is routed to a nanoantenna array through the giant electric field created by the surface states. The induced current on the nanoantennas, which contains mixing product of different optical frequency components, generates radiation at the beat frequencies of the incident photons. We utilize the functionalities of plasmon-coupled surface states to demonstrate passive wavelength conversion of nanojoule optical pulses at a 1550 nm center wavelength to terahertz regime with efficiencies that exceed nonlinear optical methods by 4-orders of magnitude.

42 ENGINEERING↗
DOE OSTI2023

Theory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons

This work proposes a photophysical phenomenon whereby ultraviolet/visible (UV/vis) excitation of a molecule involving a Franck-Condon (FC) active vibration yields infrared (IR) emission by strong coupling to an optical cavity. The resulting UV/vis-to-IR photonic down conversion process is mediated by vibrational polaritons in the electronic excited state potential. It is shown that the formation of excited state vibrational polaritons (ESVP) via UV/vis excitation only involve vibrational modes with both a non-zero FC activity and IR activity in the excited state. Density functional theory calculations are used to identify 1-Pyreneacetic acid as a molecule with this property and the dynamics of ESVP are modeled. Overall, this work introduces an avenue of polariton chemistry where excited state dynamics are influenced by the formation of vibrational polaritons. Along with this, the UV/vis-to-IR photonic down conversion is potentially useful in both sensing excited state vibrations and quantum transduction schemes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗