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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 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

Using Combustion Synthesis to Reinforce Berms and Other Regolith Structures

The Moonraker Excavator and other tools under development for use on the Moon, Mars, and asteroids will be employed to construct a number of civil engineering projects and to mine the soil. Mounds of loose soil will be subject to the local transport mechanisms plus artificial mechanisms such as blast effects from landers and erosion from surface vehicles. Some of these structures will require some permanence, with a minimum of maintenance and upkeep. Combustion Synthesis (CS) is a family of processes and techniques whereby chemistry is used to transform materials, often creating flame in a hard vacuum. CS can be used to stabilize civil engineering works such as berms, habitat shielding, ramps, pads, roadways, and the like. The method is to unroll thin sheets of CS fabric between layers of regolith and then fire the fabric, creating a continuous sheet of crusty material to be interposed among layers of loose regolith. The combination of low-energy processes, ISRU (in situ resource utilization) excavator, and CS fabrics, seems compelling as a general method for establishing structures of some permanence and utility, especially in the role of robotic missions as precursors to manned exploration and settlement. In robotic precursory missions, excavator/ mobility ensembles mine the Lunar surface, erect constructions of soil, and dispense sheets of CS fabrics that are covered with layers of soil, fired, and then again covered with layers of soil, iterating until the desired dimensions and forms are achieved. At the base of each berm, for example, is a shallow trench lined with CS fabric, fired and filled, mounded, and then covered and fired, iteratively to provide a footing against lateral shear. A larger trench is host to a habitat module, backfilled, covered with fabric, covered with soil, and fired. Covering the applied CS fabric with layers of soil before firing allows the resulting matrix to incorporate soil both above and below the fabric ply into the fused layer, developing a very irregular surface which, like sandpaper, can provide an anchor for loose soil. CS fabrics employ a coarse fiberglass weave that persists as reinforcement for the fired material. The fiberglass softens at a temperature that exceeds the combustion temperature by factors of two to three, and withstands the installation process. This type of structure should be more resistant to rocket blast effects from Lunar landers.

Rodriquez, Gary↗
DOE OSTI2015

Electrical properties of GaAs metal–oxide–semiconductor structure comprising Al{sub 2}O{sub 3} gate oxide and AlN passivation layer fabricated in situ using a metal–organic vapor deposition/atomic layer deposition hybrid system

This paper presents a compressive study on the fabrication and optimization of GaAs metal–oxide–semiconductor (MOS) structures comprising a Al{sub 2}O{sub 3} gate oxide, deposited via atomic layer deposition (ALD), with an AlN interfacial passivation layer prepared in situ via metal–organic chemical vapor deposition (MOCVD). The established protocol afforded self-limiting growth of Al{sub 2}O{sub 3} in the atmospheric MOCVD reactor. Consequently, this enabled successive growth of MOCVD-formed AlN and ALD-formed Al{sub 2}O{sub 3} layers on the GaAs substrate. The effects of AlN thickness, post-deposition anneal (PDA) conditions, and crystal orientation of the GaAs substrate on the electrical properties of the resulting MOS capacitors were investigated. Thin AlN passivation layers afforded incorporation of optimum amounts of nitrogen, leading to good capacitance–voltage (C–V) characteristics with reduced frequency dispersion. In contrast, excessively thick AlN passivation layers degraded the interface, thereby increasing the interfacial density of states (D{sub it}) near the midgap and reducing the conduction band offset. To further improve the interface with the thin AlN passivation layers, the PDA conditions were optimized. Using wet nitrogen at 600 °C was effective to reduce D{sub it} to below 2 × 10{sup 12} cm{sup −2} eV{sup −1}. Using a (111)A substrate was also effective in reducing the frequency dispersion of accumulation capacitance, thus suggesting the suppression of traps in GaAs located near the dielectric/GaAs interface. The current findings suggest that using an atmosphere ALD process with in situ AlN passivation using the current MOCVD system could be an efficient solution to improving GaAs MOS interfaces.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Honeycomb-Ordered Na 3 Ni 1.5 M 0.5 BiO 6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries

Developing high-voltage layered cathodes for sodium-ion batteries (SIBs) has always been a severe challenge. Herein, a new family of honeycomb-layered Na 3 Ni 1.5 M 0.5 BiO 6 (M = Ni, Cu, Mg, Zn) with a monoclinic superstructure has been shown to combine good Na + (de)intercalation activity with a competitive 3.3 V high voltage. By coupling the electrochemical process with ex situ X-ray absorption spectroscopy as well as in situ X-ray diffraction, the charge compensation mechanism and structural evolution of these new cathodes are clearly investigated. Interestingly, both Ni 2+ /Ni 3+ and Cu 2+ /Cu 3+ participate in the redox reaction upon cycling, and the succession of single-phase, two-phase, or three-phase regions upon Na+ extraction/insertion were identified with rather good accuracy. Furthermore, this research strategy could provide insights into the structure–function–property relationships on a new series of honeycomb-ordered materials with the general formula Na 3 Ni 1.5 M 0.5 BiO 6 and also serve as a bridge to guide future design of high-performance cathodes for SIBs.

25 ENERGY STORAGE↗
DOE OSTI2021

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2020 State-of-Technology Cases

This technical report describes the SCSAs for the production of renewable hydrocarbon transportation fuels via a range of conversion technologies in the 2020 SOTs: (1) renewable high octane gasoline (HOG) via indirect liquefaction (IDL) of woody lignocellulosic biomass (note that the IDL pathway in this SCSA represents the syngas conversion design); (2) renewable gasoline (RG) and diesel (RD) blendstocks via ex situ catalytic fast pyrolysis of woody lignocellulosic biomass; (3) RD via hydrothermal liquefaction (HTL) of wet sludge from a wastewater treatment plant; (4) renewable hydrocarbon fuels via biochemical conversion of herbaceous lignocellulosic biomass; (5) renewable diesel via HTL of a blend of algae and woody biomass; and (6) renewable diesel via combined algae processing (CAP). This technical report focuses on the environmental performance of these six biofuel production pathways in their 2020 SOT cases. The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2019 SOT cases. They also provide an opportunity to examine the impact of technology improvements in both biomass feedstock production and biofuel production that have been achieved in 2020 SOTs on the sustainability performance of these renewable transportation fuels. The SCSA results also reflect updates to Argonne National Laboratory’s Greenhouse gases, Regulated Emissions, and Energy use in Technologies (GREET ® ) model, which was released in October 2020. These GREET updates include the production of natural gas, electricity, and petroleum-based fuels that can influence biofuels’ supply chain greenhouse gas (GHG) (CO 2 , CH 4 , and N 2 O) emissions, water consumption, and air pollutant emissions. GHG emissions, water consumption, and nitrogen oxides (NO x ) emissions are the main sustainability metrics assessed in this analysis. In this analysis, we define water consumption as the amount of water withdrawn from a freshwater source that is not returned (or returnable) to a freshwater source at the same level of quality. Life-cycle fossil energy consumption and net energy balance, which is the life-cycle fossil energy consumption deducted from the renewable biofuel energy produced, are also assessed.

09 BIOMASS FUELS↗
DOE OSTI2020

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2019 State-of-Technology Cases

This technical report describes the supply chain sustainability analysis (SCSAs) for the production of renewable hydrocarbon transportation fuels via a range of conversion technologies: (1) renewable high octane gasoline (HOG) via indirect liquefaction (IDL) of woody lignocellulosic biomass (note that the IDL pathway in this SCSA represents the syngas conversion design in the 2019 SOT); (2) renewable gasoline (RG) and diesel (RD) blendstocks via ex situ catalytic fast pyrolysis of woody lignocellulosic biomass; (3) RD via hydrothermal liquefaction (HTL) of wet sludge from a wastewater treatment plant; (4) renewable hydrocarbon fuels via biochemical conversion of herbaceous lignocellulosic biomass; (5) renewable diesel via HTL of a blend of algae and woody biomass; and (6) renewable diesel via combined algae processing (CAP). This technical report focuses on the environmental performance of these six biofuel production pathways in their 2019 SOT cases. The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2018 SOT cases. They also provide an opportunity to examine the impact of technology improvements in both biomass feedstock production and biofuel production that have been achieved in 2019 SOTs on the sustainability performance of these renewable transportation fuels, and they reflect updates to Argonne National Laboratory’s Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET®) model, which was released in October 2019. These GREET updates include the production of natural gas, electricity, and petroleum-based fuels that can influence biofuels’ supply chain greenhouse gas (GHG) (CO₂, CH₄, and N₂O) emissions, water consumption, and air pollutant emissions. GHG emissions, water consumption, and nitrogen oxides (NO x ) emissions are the main sustainability metrics assessed in this analysis. In this analysis, we define water consumption as the amount of water withdrawn from a freshwater source that is not returned (or returnable) to a freshwater source at the same level of quality. Life-cycle fossil energy consumption and net energy balance, which is the life-cycle fossil energy consumption deducted from the renewable biofuel energy produced, are also assessed.

09 BIOMASS FUELS↗
DOE OSTI2022

Uncertainties Induced by Processing Parameter Variation in Selective Laser Melting of Ti6Al4V Revealed by In-Situ X-ray Imaging

Selective laser melting (SLM) additive manufacturing (AM) exhibits uncertainties, where variations in build quality are present despite utilizing the same optimized processing parameters. In this work, we identify the sources of uncertainty in SLM process by in-situ characterization of SLM dynamics induced by small variations in processing parameters. We show that variations in the laser beam size, laser power, laser scan speed, and powder layer thickness result in significant variations in the depression zone, melt pool, and spatter behavior. On average, a small deviation of only ~5% from the optimized/reference laser processing parameter resulted in a ~10% or greater change in the depression zone and melt pool geometries. For spatter dynamics, small variation (10 μm, 11%) of the laser beam size could lead to over 40% change in the overall volume of the spatter generated. The responses of the SLM dynamics to small variations of processing parameters revealed in this work are useful for understanding the process uncertainties in the SLM process.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2018 State-of-Technology Cases and Design Cases

This technical report describes the SCSAs for the production of renewable hydrocarbon transportation fuels via a range of conversion technologies: (1) renewable high octane gasoline (HOG) via indirect liquefaction (IDL) of woody lignocellulosic biomass (note that the IDL pathway in this SCSA represents the syngas conversion design in the 2018 SOT and 2022 design cases [Tan et al., 2018]); (2) renewable gasoline (RG) and diesel (RD) blendstocks via ex situ catalytic fast pyrolysis of woody lignocellulosic biomass; (3) RD via hydrothermal liquefaction (HTL) of wet sludge from a wastewater treatment plant; (4) renewable hydrocarbon fuels via biochemical conversion of herbaceous lignocellulosic biomass; (5) renewable diesel via HTL of a blend of algae and woody biomass; and (6) renewable diesel via combined algae processing (CAP). This technical report focuses on the environmental performance of these six biofuel production pathways in their 2018 SOT cases, as well as in their design cases (future target projections). The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2015 and 2016 SOT cases (Edward Frank et al. 2016; Hao Cai et al. 2016, 2017; Cai et al. 2018) in the case of IDL, algae CAP, and biochemical conversion pathways. They also provide an opportunity to examine the impact of technology improvements in both biomass feedstock production and biofuel production that have been achieved in 2018 SOTs on the sustainability performance of these renewable transportation fuels, and they reflect updates to Argonne National Laboratory’s Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET®) model, which was released in October 2018 (Wang et al. 2018). These GREET updates include production of natural gas, electricity, and petroleum-based fuels that can influence biofuels’ supply chain greenhouse gas (GHG) (CO2, CH4, and N2O) emissions, water consumption and air pollutant emissions. GHG emissions, water consumption, and 2 nitrogen oxides (NOx) emissions are the main sustainability metrics assessed in this analysis. In this analysis, we define water consumption as the amount of water withdrawn from a freshwater source that is not returned (or returnable) to a freshwater source at the same level of quality. Life-cycle fossil energy consumption and net energy balance, which is the life-cycle fossil energy consumption deducted from the renewable biofuel energy produced, are also assessed.

02 PETROLEUM↗
DOE OSTI2018

Supply Chain Sustainability Analysis of Renewable Hydrocarbon Fuels via Indirect Liquefaction, Ex Situ Catalytic Fast Pyrolysis, Hydrothermal Liquefaction, Combined Algal Processing, and Biochemical Conversion: Update of the 2018 State-of-Technology Cases and Design Cases

This technical report describes the SCSAs for the production of renewable hydrocarbon transportation fuels via a range of conversion technologies: (1) renewable high octane gasoline (HOG) via indirect liquefaction (IDL) of woody lignocellulosic biomass (note that the IDL pathway in this SCSA represents the syngas conversion design in the 2018 SOT and 2022 design cases [Tan et al., 2018]); (2) renewable gasoline (RG) and diesel (RD) blendstocks via ex situ catalytic fast pyrolysis of woody lignocellulosic biomass; (3) RD via hydrothermal liquefaction (HTL) of wet sludge from a wastewater treatment plant; (4) renewable hydrocarbon fuels via biochemical conversion of herbaceous lignocellulosic biomass; (5) renewable diesel via HTL of a blend of algae and woody biomass; and (6) renewable diesel via combined algae processing (CAP). This technical report focuses on the environmental performance of these six biofuel production pathways in their 2018 SOT cases, as well as in their design cases (future target projections). The results of these renewable hydrocarbon fuel pathways in these SCSA analyses update those for the respective 2015 and 2016 SOT cases (Edward Frank et al. 2016; Hao Cai et al. 2016, 2017; Cai et al. 2018) in the case of IDL, algae CAP, and biochemical conversion pathways. They also provide an opportunity to examine the impact of technology improvements in both biomass feedstock production and biofuel production that have been achieved in 2018 SOTs on the sustainability performance of these renewable transportation fuels, and they reflect updates to Argonne National Laboratory's Greenhouse gases, Regulated Emissions, and Energy use in Transportation (GREET[R]) model, which was released in October 2018 (Wang et al. 2018). These GREET updates include production of natural gas, electricity, and petroleum-based fuels that can influence biofuels' supply chain greenhouse gas (GHG) (CO 2 , CH 4 , and N 2 O) emissions, water consumption and air pollutant emissions. GHG emissions, water consumption, and 2 nitrogen oxides (NO x ) emissions are the main sustainability metrics assessed in this analysis. In this analysis, we define water consumption as the amount of water withdrawn from a freshwater source that is not returned (or returnable) to a freshwater source at the same level of quality. Life-cycle fossil energy consumption and net energy balance, which is the life-cycle fossil energy consumption deducted from the renewable biofuel energy produced, are also assessed.

09 BIOMASS FUELS↗
DOE OSTI2022

Process design for calcination of nickel-based cathode materials by in situ characterization and multiscale modeling

Developing battery materials towards commercial use, from the early discovery through synthesis, processing, scaling up, and eventually to industrial production, may take decades. A notable example is Ni-based layered oxides, which were discovered as early as 1950s and intensively pursued as cathode active materials (CAMs) since the early 90s but have yet to realize their full commercial potential. Significant efforts have been devoted to materials development aiming at improving performance, far less to process development for large-scale synthesis and processing of CAMs. In this paper, we present a rational design of calcination for scalable production of Ni-based CAMs. We start with an overview of the current understanding and knowledge gaps hindering rational process design and scaling-up of the calcination process. Then with specific examples, we demonstrate how to tackle those fundamental challenges through in situ characterization and multiscale modeling. Finally, we conclude by providing perspectives on the remaining challenges and emerging opportunities in commercial development of Ni-based cathodes, calling for more endeavors in this field.

25 ENERGY STORAGE↗
DOE OSTI2018

Assessment of shallow subsea hydrocarbons as a proxy for leakage at offshore geologic CO 2 storage sites

We report this study is part of a multi-phase effort to identify and characterize offshore geological carbon storage (GCS) potential along the Texas Gulf Coast. Previous efforts acquired a high-resolution 3D seismic dataset (P-cable™) and interpreted a seismically discontinuous zone as shallow gas pockets (<100 m below seafloor) associated with a vertical chimney structure. Our approach was to measure hydrocarbon concentrations and stable carbon isotopes near the seafloor to assess if gas migrated vertically from seismic anomalies. Deep-sourced thermogenic hydrocarbons would indicate that the structure is transmissive which could indicate an unacceptable risk for GCS at the site. Alternatively, hydrocarbons formed in-situ from biogenic processes would not preclude transmissivity of the structure but would add information to the risk assessment. Gases were extracted from 23 piston core samples recovered between 2.56 and 3.50 m subseafloor. Light hydrocarbons and stable carbon isotopes of methane were used for source attribution. The result was that geochemical signatures were consistent with typical background values observed within the first few meters of subsea sediment and therefore did not indicate leakage from depth. From our analysis, we offer insights into the use of hydrocarbon molecular and isotopic compositions at the seafloor for signal attribution as part of environmental assessments at geological CO 2 storage sites.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Dense Ru single-atoms integrated with sulfoacids for cellulose valorization to isosorbide

Metal-acid bifunctional catalysts are the unity of two opposites (metal-acid repelling) for cellulosic biomass valorization to isosorbide. It is challenging to improve the selectivity of metal hydrogenation catalysts and their synergism with acids for catalytic hydrolysis and dehydration to achieve substantial isosorbide. Herein, dense Ru single-atoms (10.1 wt% of Ru SAs) are anchored on sulfoacid-functionalized hollow mesoporous carbon shells, designed by assembling silica and 8-hydroxyquinoline-modified chitosan (HQ-CTS) through in situ Stöber templating strategy before pyrolysis and acid treatment. Based on X-ray absorption fine structure and computational modeling results, the structure of Ru SAs is determined as RuN 4 , which is more selective for a transitional glucose hydrogenation to sorbitol than Ru001 of Ru clusters. A lower-energy barrier of 1.21 (0.72) eV is delivered over RuN 4 (Ru001) for glucose hydrogenation (isomerization). These Ru SAs are integrated with sulfoacids (SO 3 H) but resistent against acids, rendering enhanced isosorbide yield in water as compared to Ru clusters, via a one-pot cascade reaction under harsh conditions (220 °C, 6 MPa H 2 ). The elaborately fabricated dense Ru SAs and sulfoacids, achieved by varying the addition time of HQ-CTS during the in situ Stöber templating process, improve the synergism of glucose hydrogenation with cellulose hydrolysis and sorbitol dehydration. In conclusion, this study provides a new idea for rational design of high-performance metal-acid bifunctional catalysts toward one-pot conversion of cellulose to isosorbide.

36 MATERIALS SCIENCE↗
DOE OSTI2023

In situ synchrotron X-ray diffraction analysis of ultrasonically assisted microstructure refinement during laser melting process

This work investigates the effect of ultrasonic treatment (UST) on the microstructure of AA4043 alloy during laser melting process. Here, the study utilizes in situ synchrotron X-ray diffraction (SXRD) and postmortem electron backscatter diffraction (EBSD) techniques to examine the ultrasonic grain refinement mechanism. The SXRD diffraction patterns exhibit higher continuity of major diffraction rings in the UST-test pattern, indicating a more refined grain structure. The presence of new diffraction spots in the post-test diffraction pattern with UST suggests the breakdown of epitaxial growth of columnar dendrites during solidification. Thermal profiles determined by analyzing the lattice parameter evolution show a faster cooling rate with UST. The inverse pole figures and aspect ratio distribution from EBSD reveal that the UST samples exhibit a refined, more equiaxed grain structure along the weld centerline. UST sample also develops more fine-sized low angle grain boundaries (LAGBs). These features offer better hot-cracking resistance in aluminum alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Development of arsenic doped Cd(Se,Te) absorbers by MOCVD for thin film solar cells

Recent developments in CdTe solar cell technology have included the incorporation of ternary alloy Cd(Se,Te) in the devices. CdTe absorber band gap grading due to Se alloying contributes to current density enhancement and can result in device performance improvement. Here we report Cd(Se,Te) polycrystalline thin films grown by a chamberless inline atmospheric pressure metal organic chemical vapour deposition technique, with subsequent incorporation in CdTe solar cells. The compositional dependence of the crystal structure and optical properties of Cd(Se,Te) are examined. Selenium graded Cd(Se,Te)/CdTe absorber structure in devices are demonstrated using either a single CdSe layer or CdSe/Cd(Se,Te) bilayer (with or without As doping in the Cd(Se,Te) layer). Cross-sectional TEM/EDS, photoluminescence spectra and secondary ion mass spectroscopy analysis confirmed the formation of a graded Se profile toward the back contact with a diffusion length of ~1.5 um and revealed back-diffusion of Group V (As) dopants from the CdTe layer into Cd(Se,Te) grains. Due to the strong Se/Te interdiffusion, CdSe in the Se bilayer configuration was unable to form an n-type emitter layer in processed devices. In situ As doping of the Cd(Se,Te) layer benefited the device junction quality with current density reaching 28.3 mA/cm 2 . The results provide useful insights for the optimisation of Cd(Se,Te)/CdTe solar cells.

14 SOLAR ENERGY↗
DOE OSTI2020

High-Resolution Laser-Induced Graphene. Flexible Electronics beyond the Visible Limit

Laser-induced graphene (LIG) is a multifunctional graphene foam that is commonly direct-written with an infrared laser into a carbon-based precursor material. Here, a visible 405 nm laser is used to directly convert polyimide into LIG. This enabled the formation of LIG with a spatial resolution of ~12 μm and a thickness of <5 μm. The spatial resolution enabled by the relatively smaller focused spot size of the 405 nm laser represents a >60% reduction in LIG feature sizes reported in prior publications. This process occurs in situ in an SEM chamber, thus allowing direct observation of LIG formation. The reduced size of the LIG features enables the direct-write formation of flexible electronics that are not visible to the unaided eye. A humidity sensor is demonstrated which could detect human breath with a response time of 250 ms. With the growing interest in LIG for flexible electronics and sensors, finer features can greatly expand its utility.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Dynamic Transformation of High-Architectural Nanocrystal Superlattices upon Solvent Molecule Exposure

The cluster-based body-centered-cubic superlattice (cBCC SL) represents one of the most complicated structures among reported nanocrystal assemblies, comprised of 72 truncated tetrahedral quantum dots per unit cell. Our previous report revealed that truncated tetrahedral quantum dots within cBCC SLs possessed highly controlled translational and orientational order owing to an unusual energetic landscape based on the balancing of entropic and enthalpic contributions during the assembly process. However, the cBCC SL’s structural transformability and mechanical properties, uniquely originating from such complicated nanostructures, have yet to be investigated. Herein, we report that cBCC SLs can undergo dynamic transformation to face-centered-cubic SLs in response to post-assembly molecular exposure. We monitored the dynamic transformation process using in situ synchrotron-based small-angle X-ray scattering, revealing a dynamic transformation involving multiple steps underpinned by interactions between incoming molecules and TTQDs’ surface ligands. Furthermore, our mechanistic study demonstrated that the precise configuration of TTQDs’ ligand molecules in cBCC SLs was key to their high structural transformability and unique jelly-like soft mechanical properties. While ligand molecular configurations in nanocrystal SLs are often considered minor features, our findings emphasize their significance in controlling weak van der Waals interactions between nanocrystals within assembled SLs, leading to previously unremarked superstructural transformability and unique mechanical properties. Finally, our findings promote a facile route toward further creation of soft materials, nanorobotics, and out-of-equilibrium assemblies based on nanocrystal building blocks.

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

Formation, chemical evolution and solidification of the dense liquid phase of calcium (bi)carbonate

Metal carbonates, which are ubiquitous in the near-surface mineral record, are a major product of biomineralizing organisms and serve as important targets for capturing anthropogenic CO 2 emissions. However, pathways of carbonate mineralization typically diverge from classical predictions due to the involvement of disordered precursors, such as the dense liquid phase (DLP), yet little is known about DLP formation or solidification processes. Using in situ methods we report that a highly hydrated bicarbonate DLP forms via liquid–liquid phase separation and transforms into hollow hydrated amorphous CaCO 3 particles. Acidic proteins and polymers extend DLP lifetimes while leaving the pathway and chemistry unchanged. Molecular simulations suggest that the DLP forms via direct condensation of solvated Ca 2+ •(HCO 3 – ) 2 complexes that react due to proximity effects in the confined DLP droplets. Furthermore, our findings provide insight into CaCO 3 nucleation that is mediated by liquid–liquid phase separation, advancing the ability to direct carbonate mineralization and elucidating an often-proposed complex pathway of biomineralization.

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

A single-Pt-atom-on-Ru-nanoparticle electrocatalyst for CO-resilient methanol oxidation

Single Pt atom catalysts are key targets because a high exposure of Pt substantially enhances electrocatalytic activity. In addition, PtRu alloy nanoparticles are the most active catalysts for the methanol oxidation reaction. To combine the exceptional activity of single Pt atom catalysts with an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. In this report we demonstrate a process that grows and spreads Pt islands on Ru branched nanoparticles to create single-Pt-atom-on-Ru catalysts. By following the spreading process by in situ TEM, we found that the formation of a stable single atom structure is thermodynamically driven by the formation of strong Pt–Ru bonds and the lowering of the surface energy of the Pt islands. The stability of the single-Pt-atom-on-Ru structure and its resilience to CO poisoning result in a high current density and mass activity for the methanol oxidation reaction over time.

36 MATERIALS SCIENCE↗