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Results for “highly selective”

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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Synthesis of core/shell nanocrystals with ordered intermetallic single-atom alloy layers for nitrate electroreduction to ammonia

Structurally ordered intermetallic nanocrystals (NCs) and single-atom catalysts (SACs) are two emerging catalytic motifs for sustainable chemical production and energy conversion. However, both have synthetic limitations which can lead to the aggregation of NCs or metal atoms. Single-atom alloys (SAAs), which contain isolated metal atoms in a host metal, can overcome the aggregation concern because of the thermodynamic stabilization of single atoms on host metal surfaces. We report a direct solution-phase synthesis of Cu/CuAu core/shell NCs with tunable SAA layers. This synthesis can be extended to other Cu/CuM (M = Pt, Pd) systems, in which M atoms are isolated in the copper host. Using this method, the density of SAAs on a copper surface can be controlled, resulting in both low and high densities of single atoms. Alloying gold into the copper matrix introduced ligand effects that optimized the chemisorption of *NO 3 and *N. As a result, the densely packed Cu/CuAu material demonstrated a high selectivity toward NH 3 from the electrocatalytic nitrate reduction reaction with an 85.5% Faradaic efficiency while maintaining a high yield rate of 8.47 mol h -1 g -1 . This work advances the design of atomically precise catalytic sites by creating core/shell NCs with SAA atomic layers, opening an avenue for broad catalytic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Catalytic co-pyrolysis of LDPE and PET with HZSM-5, H-beta, and HY: experiments and kinetic modelling

In this study, the catalytic pyrolysis of low-density polyethylene (LDPE), polyethylene terephthalate (PET) and their mixture (1 : 1 wt/wt) with three zeolite catalysts (HZSM-5, H-beta, HY) was investigated using a thermogravimetric analyzer (TGA) and a Pyroprobe® micro-reactor coupled to a gas chromatograph mass spectrometer (Py-GC/MS). The TGA results demonstrated that during pyrolysis at 10 °C min –1 , on average, zeolite catalysts decreased the maximum decomposition temperature by 149 °C for LDPE while only decreasing by 8 °C for PET. The derivative thermogravimetric (DTG) curve evidenced interactions when the two polymers were catalytically co-pyrolyzed for all the three catalysts. A lumped nth order reaction scheme was able to accurately model both non-catalytic and catalytic pyrolysis and co-pyrolysis by using the least squares fitting approach for determining the kinetic parameters. The kinetic model was able to model well the interaction effects observed during catalytic co-pyrolysis of LDPE and PET with HZSM-5, H-beta, and HY (Fit% Wt% > 96%, Fit% DTG > 94%). Py-GC/MS experiments for the catalytic fast pyrolysis of LDPE revealed that HZSM-5 resulted in the highest selectivity to aromatic hydrocarbons (31.6%) and HY resulted in the highest selectivity to gasoline range C 5 –C 10 paraffins and olefins (40.9%). Catalytic fast pyrolysis of PET showed high selectivity to benzene for all the catalysts (>43%) and that HZSM-5 resulted in the highest selectivity to polyaromatic hydrocarbons (24.7%). Finally, the catalytic fast co-pyrolysis of LDPE and PET revealed interaction effects for all the three catalysts evidenced by a positive synergy% for alkylated benzenes (3–142%) and polyaromatics (105–187%) with a concomitant negative synergy% for benzene (24–36%) and C 5 –C 10 paraffins and olefins (27–53%).

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

BLUP and mean yields of selected top 25 high yielding half-sib families

BLUP and mean yields of selected top 25 high yielding half-sib families. The yield BLUP were estimated using mixed linear models. The family column indicates the families with progeny column showing the corresponding progenies to selected families. ‘Wat’ here has been used to denote Watkinsville, ‘Tif’ for Tifton and ‘TN’ for Tennessee.

09 BIOMASS FUELS↗
DOE OSTI2020

Moderate pH changes alter the fluxes, selectivities and limiting currents in ion transport through polyelectrolyte multilayers deposited on membranes

Layer-by-layer (LBL) polyelectrolyte coatings on membranes are attractive for their high selectivities between monovalent and divalent ions. However, deposition of poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films on ion-exchange membranes leads to low ion fluxes that restrict productivity or current efficiency. This study shows that increasing the solution pH from 6.5 to 8.3 enhances cation fluxes and limiting currents through (PAH/PSS) 5 PAH-coated cation-exchange membranes while still achieving order of magnitude selectivity increases compared to bare membranes. In Donnan dialysis through (PAH/PSS) 5 PAH-coated Nafion, at pH 8.3 the K + /Mg 2+ selectivity is 100, and the K + flux is 22 times that at pH 6.5. Moreover, at the higher pH the electrodialysis limiting current through these membranes increases ~5-fold. This enables electrodialysis separation of K + and Mg 2+ with a current efficiency around 0.75, a selectivity of 18, and 50% K + recovery from the source phase. Transmembrane potential measurements and increases in Cl - /SO 4 2- selectivities (from 9.5 at pH 6.5 to ~70 at pH 8.3) for porous alumina membranes coated with (PSS/PAH) 5 PSS films suggest that the coating becomes cation-permselective at higher pH. Increased cation transference numbers in polyelectrolyte coatings likely lead to the enhanced limiting currents for coated Nafion at higher pH. Lastly, (PAH/PSS) 5 PAH-coated Nafion shows a Li + /Mg 2+ Donnan dialysis selectivity >700 at neutral pH and a selectivity of 10 at pH 8.3. However, the Li + flux is 6 times greater at pH 8.3, which might make operation at the higher pH desirable.

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

Applications of targeted proteomics in metabolic engineering: advances and opportunities

Optimization of metabolically engineered organisms requires good understanding of producing balanced level of pathway proteins. Targeted proteomics via selected-reaction monitoring (SRM) has been increasingly used in metabolic engineering studies to detect and quantify sets of proteins with high selectivity, multiplexity, and reproducibility. In combination with metabolomics and other omics tools, targeted proteomics has helped optimize the production of many bio-based chemicals in various metabolic engineering cell factories. In this review, we present recent applications of targeted proteomics in metabolic engineering studies and highlight several successful cases of targeted proteomics in boosting production of commodity and high value chemicals. Additionally, we also discuss challenges and limitations of current targeted proteomics and map opportunities for future research.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Genomic signatures in Variovorax enabling colonization of the Populus endosphere

Microbial colonization of plant roots involves strong selective pressures that shape the structure and function of root-associated communities. In particular, the endosphere represents a highly selective environment requiring host entry and in planta persistence. However, strain-specific microbial traits that enable endosphere colonization remain poorly understood. Here, we use a defined, genome-resolved community of 28 Variovorax strains isolated from the roots of Populus deltoides and Populus trichocarpa (poplar trees) to determine which strains partition between rhizosphere and endosphere compartments and to identify the genomic traits associated with endosphere specialization. By combining strain-resolved metagenomic profiling, comparative genomics, and functional assays, we demonstrate that dominant endosphere colonizers are enriched in genes related to nutrient metabolism, redox balance, transcriptional regulation, and a conserved L-fucose utilization pathway experimentally shown to enhance root colonization. Not all strains succeed through the same strategy. Community-wide functional profiling revealed a distinct and reduced set of traits in the endosphere, including orthogroups associated with low-abundance strains that were overlooked in strain-level analyses. These findings reveal that multiple ecological strategies, such as metabolic competition, regulatory adaptation, and niche specialization, can support endosphere colonization. Our results advance the understanding of how bacterial colonization traits are distributed and deployed within a plant microbiome and suggest that host filtering selects for distinct, and sometimes complementary, microbial strategies. This work supports a shift toward mechanistic, genome-resolved models of microbiome assembly and offers a framework for linking microbial function to host colonization success.

comparative genomics↗
DOE OSTI2024

Metal Organic Frameworks for Noble Gas Isotope Harvesting at FRIB (Final Technical Report)

This project was a collaborative effort between Lawrence Livermore National Laboratory (LLNL) and Michigan State University (MSU) to investigate the use of promising metal organic frameworks (MOFs) for radioactive noble gas capture, with a focus on harvesting exotic radiokryptons from FRIB. After screening several candidate materials, two MOFs were selected for testing: SIFSIX-3Cu and SBMOF-1. Further evaluation showed that although SIFSIX-3Cu has a high selectivity for Kr, SBMOF-1 is less sensitive to the humidity that is present in the FRIB harvesting system and is more readily integrated into the harvesting infrastructure. SBMOF-1 was then evaluated for temperature-dependent Kr and Xe uptake in order to determine the sorption enthalpy. The SBMOF-1 data led to the design of a noble gas capture system that will be fabricated and put into service for isotope harvesting at FRIB as part of a separate project.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Dimethyl Carbonate: Review of Synthesis Routes and Catalysts Used

This review summarizes the performance of potential catalysts for the synthesis of dimethyl carbonate (DMC) using CO2 as a feedstock by two major processes—the direct route of carbonylation of alcohols and the indirect route of alcoholysis of urea. The reaction mechanisms and corresponding catalysts that were previously investigated are discussed. The major challenges associated with the conversion of CO2 to DMC are the low yields, low DMC selectivity, and thermodynamic limitations (alcohol carbonylation) of reversible reactions with low equilibrium constants. This occurs mainly due to the highly stable carbon dioxide molecules. The development of novel catalysts with high yields and high selectivity needs to be studied to overcome these technical challenges. In addition, to enhance the DMC yield, the use of dehydrating agents for water removal from the reaction mixture is recommended and discussed in detail in this article. This review critically examines the different catalysts used by investigators, along with their respective operating conditions and suitability in applications for the commercial synthesis of CO2-based DMC.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Selective Binding and Light-Driven Release of Fluorous PF 6 – and Radioactive 99 TcO 4 – Anions for All-to-Nothing Liquid–Liquid Extraction

The removal of anions from aqueous media using molecular receptors in liquid–liquid extraction is a long-standing strategy to clean up contaminated water sources. Therein, high selectivity is needed to remove specific ions from mixtures of other ions, and high affinity provides extractions at low concentrations. However, the high affinity creates a conundrum by impeding the release of the ions in any stripping steps needed for further processing. To circumvent this problem, light-responsive receptors have been proposed as candidates for turning off the binding, but they are currently untested in liquid–liquid extraction. We tested the feasibility of light-driven release using a cyanostar macrocycle. We demonstrate the selective extraction of PF$^{–}_{6}$ anions over large excesses of competing anions (Cl – , NO$^{–}_{3}$, SO$^{2–}_{4}$) followed by photodriven release for quantitative isolation of the target. Release relies on photoisomerization of the macrocycle’s five stilbenes generating distorted isomers to turn off binding. With modest reversibility, only a single-shot release was demonstrated, akin to photodriven uncaging. These methods were extended to the capture and photodriven release of ReO$^{–}_{4}$ and radioactive 99 TcO$^{–}_{4}$ anions at ∼90% efficiency. Extraction was demonstrated down to the highly dilute 4 ppb levels of the 99 TcO$^{–}_{4}$ anion. Furthermore, this proof-of-concept demonstration verifies the use of a large change in affinity for the all-to-nothing capture and release of target anions between liquid phases.

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

Atomically Dispersed Ni‐N‐C Catalysts for Electrochemical CO 2 Reduction

Abstract The atomic dispersion of nickel in Ni‐N‐C catalysts is key for the selective generation of carbon monoxide through the electrochemical carbon dioxide reduction reaction (CO 2 RR). Herein, the study reports a highly selective, atomically dispersed Ni 1.0% ‐N‐C catalyst with reduced Ni loading compared to previous reports. Extensive materials characterization fails to detect Ni crystalline phases, reveals the highest concentration of atomically dispersed Ni metal, and confirms the presence of the proposed Ni‐N x active site at this reduced loading. The catalyst shows excellent activity and selectivity toward CO generation, with a faradaic efficiency for CO generation (FE CO ) of 97% and partial current density for CO (j co ) of ‐9.0 mA cm −2 at ‐0.9 V in an electrochemical H‐type cell. CO 2 RR activity and selectivity are also studied by rotating disk electrode (RDE) measurements where transport limitations can be suppressed. It is expected that the utility of these Ni‐N‐C catalysts will lie with tandem CO 2 RR reaction schemes to multi‐carbon (C 2+ ) products.

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

Tailoring the Structure of Carbon Molecular Sieves Derived from an Aromatic Polyamide

Energy-efficient and selective separation technologies are required to reclaim aqueous waste streams for reuse. Carbon molecular sieves (CMS) are one material capable of separating organic solvent and gaseous mixtures due to the presence of permanent, rigid, and molecular sieving pores and could potentially be used in aqueous separations. Here, a novel CMS material is derived from an aromatic polyamide precursor with tailored fabrication techniques. Structural characteristics of this CMS have been probed with various analyses and are potentially ideal for selective separations as adsorbents. In this work, elemental analyses provide insight about the potential chemical structures of CMS materials that result from degradation mechanisms. Gravimetric sorption data is used to estimate sorption, diffusion, and permeability selectivity with water and N, N-dimethylformamide. While challenges to the development and implementation of such carbonaceous materials remain, highly selective materials are critical starting points for enabling ultra-challenging separation processes of the future.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Prediction of stability constants of metal–ligand complexes by machine learning for the design of ligands with optimal metal ion selectivity

The new LOGKPREDICT program integrates HostDesigner molecular design software with the machine learning (ML) program Chemprop. By supplying HostDesigner with predicted log K values, LOGKPREDICT enhances the computer-aided molecular design process by ranking ligands directly by metal–ligand binding strength. Harnessing reliable experimental data from a historic National Institute of Standards and Technology (NIST) database and data from the International Union of Pure and Applied Chemistry (IUPAC), we train message passing neural net algorithms. The multi-metal NIST-based ML model has a root mean square error (RMSE) of 0.629 ± 0.044 (R 2 of 0.960 ± 0.006), while two versions of lanthanide-only IUPAC-based ML models have, respectively, RMSE of 0.764 ± 0.073 (R 2 of 0.976 ± 0.005) and 0.757 ± 0.071 (R 2 of 0.959 ± 0.007). For relative log K predictions on an out-of-sample set of six ligands, demonstrating metal ion selectivity, the RMSE value reaches a commendably low 0.25. Here we showcase the use of LOGKPREDICT in identifying ligands with high selectivity for lanthanides in aqueous solutions, a finding supported by recent experimental evidence. We also predict new ligands yet to be verified experimentally. Therefore, our ML models implemented through LOGKPREDICT and interfaced with the ligand design software HostDesigner pave the way for designing new ligands with predetermined selectivity for competing metal ions in an aqueous solution.

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

Understanding Inlet Concentration Effects on the Electrocatalytic Conversion of CO 2 to Formic Acid in Gas-Fed Electrolyzers

The electrochemical CO 2 reduction reaction (CO2RR) to produce value-added products remains a developing technology for utilizing waste CO 2 streams. Most device-level CO2RR studies use pure CO 2 gas feeds; however, the effect of dilute CO 2 on the electrolyzer performance is an important consideration for large-scale electrolyzer operation, single-pass conversion, and real-world CO 2 source utilization. This work investigates the effect that the CO 2 concentration has on the performance of formic acid (HCOOH) producing tin oxide (SnO 2 ) and bismuth oxide (Bi 2 O 3 ) catalysts in an electrolyzer device setting. Surprisingly, SnO2 demonstrated an approximately 20% increase in HCOOH selectivity (Faradaic efficiency) when the CO 2 concentration decreased from 100 to 20%. In contrast, Bi 2 O 3 consistently demonstrated high selectivity toward HCOOH across the same CO 2 concentration range. The effects of the CO 2 concentration on selectivity were further investigated with half-cell experiments and in situ Raman spectroscopy, which revealed dynamic changes in the cathodic overpotential and chemical state of the catalyst that depended on the CO 2 concentration. Density functional theory calculations showed how changes in the surface oxidation state of Sn, varying from fully oxidized SnO 2 to metallic Sn(0), affect the thermodynamic barriers of the three main observed products: HCOOH, CO, and H 2 . Our results indicate that dilute CO 2 concentrations required larger cathodic overpotentials to sustain a fixed current density, which, in turn, pushed the Sn-based catalyst toward a more reduced surface that was favorable to HCOOH formation. On the other hand, the Bi-based catalyst remained in a metallic state at CO2RR-relevant potentials and demonstrated a consistent product selectivity regardless of CO 2 concentration. These findings highlight how varying the CO 2 inlet gas concentrations affects the chemical state of catalysts and the resulting performance metrics.

42 ENGINEERING↗
DOE OSTI2024

Mechanistic Insights into the Origins of Selectivity in a Cu-Catalyzed C–H Amidation Reaction

The catalytic transformation of C-H to C-N bonds offers rapid access to fine chemicals and high-performance materials, but achieving high selectivity from undirected aminations of unactivated C(sp 3 )-H bonds remains an outstanding challenge. Here, we report the origins of the reactivity and selectivity of a Cu-catalyzed C-H amidation of simple alkanes. Using a combination of experimental and computational mechanistic studies and energy decomposition techniques, we uncover a switch in mechanism from inner-sphere to outer-sphere coupling between alkyl radicals and the active Cu(II) catalyst with increasing substitution of the alkyl radical. The combination of computational predictions and detailed experimental validation shows that simultaneous minimization of both Cu-C covalency and alkyl radical size increases the rate of reductive elimination and that both strongly electron-donating and electron-withdrawing substituents on the catalyst accelerate the selectivity-determining C-N bond formation process as a result of a change in mechanism. These findings offer design principles for the development of improved catalyst scaffolds for radical C-H functionalization reactions.

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

Cyclodextrin-Derived Porous Liquids Enabled by In Situ Solvation Shell Formation

Porous liquids (PLs) represent a unique platform for molecular separations by combining permanent porosity with liquid-phase mobility. However, it remains a formidable challenge to construct and stabilize PLs with sub-5 Å pores using readily available porous host and liquid media. Here, we report the construction of cyclodextrin (CD)-derived PLs enabled by in situ solvation shell formation. The acid–base neutralization reaction between CD and an organic base was leveraged to generate a thin ionic solvation shell around the CD host, effectively liquefying CD and preventing its segregation in the liquid base medium while preserving accessible molecular-scale cavities. Spectroscopic analysis, neutron scattering, density functional theory calculations, and molecular dynamics simulations collectively confirm the structural evolution and existence of abundant internal porosity in PLs. The unique architectures of CD-derived PLs enable highly selective encapsulation of fluorinated alkanes and significantly enhanced uptake of inert gases. This facile and generalizable strategy enables construction of high-quality PLs with engineered ultramicroporosity to facilitate molecular separations.

Cavities↗
DOE OSTI2025

Sustainable Graphite and Jet Fuel from Biorefinery Residue

Abstract Battery‐grade graphite and aviation fuel are traditionally produced from non‐renewable, fossil carbon feedstocks and result in substantial greenhouse gas emissions. Biomass holds exciting potential as a renewable and sustainable feedstock for the production of graphite and aviation fuel, but challenges exist including the necessity of a catalyst when producing graphite and low selectivity when producing aviation fuel. A process to convert a biomass‐derived feedstock into graphite without the use of a catalyst and fuels with high selectivity towards sustainable aviation fuel (SAF) is innovated. Heavy bio‐oil undergoes a conversion process similar to the commercial production of synthetic graphite including coking at 500 °C, calcination at 1000 °C, and graphitization at 2800 °C. The resulting biographite exhibits excellent performance in lithium‐ion battery configurations with specific capacity of ~330 mAh g −1 and a 96.8 % capacity rebound after high rate cycling. The liquid hydrocarbon co‐product from coking is suitable for hydrotreating into SAF. The aviation fuel fraction (70 wt % of the fuel produced) meets ASTM standards and is composed primarily of cycloalkanes (~80 wt %) which improves energy density compared to paraffins produced by other SAF pathways and may replace aromatics for elastomer swelling in traditional jet fuel with less soot production.

09 BIOMASS FUELS↗
DOE OSTI2023

Monobody Inhibitor Selective to the Phosphatase Domain of SHP2 and its Use as a Probe for Quantifying SHP2 Allosteric Regulation

SHP2 is a phosphatase/adaptor protein that plays an important role in various signaling pathways. Its mutations are associated with cancers and developmental diseases. SHP2 contains a protein tyrosine phosphatase (PTP) and two SH2 domains. Selective inhibition of these domains has been challenging due to the multitude of homologous proteins in the proteome. Here, we developed a monobody, synthetic binding protein, that bound to and inhibited the SHP2 PTP domain. It was selective to SHP2 PTP over close homologs. A crystal structure of the monobody-PTP complex revealed that the monobody bound both highly conserved residues in the active site and less conserved residues in the periphery, rationalizing its high selectivity. Its epitope overlapped with the interface between the PTP and N-terminal SH2 domains that is formed in auto-inhibited SHP2. By using the monobody as a probe for the accessibility of the PTP active site, we developed a simple, nonenzymatic assay for the allosteric regulation of SHP2. The assay showed that, in the absence of an activating phospho-Tyr ligand, wild-type SHP2 and the “PTP-dead” C459E mutant were predominantly in the closed state in which the PTP active site is inaccessible, whereas the E76K and C459S mutants were in the open, active state. It also revealed that previously developed monobodies to the SH2 domains, ligands lacking a phospho-Tyr, weakly favored the open state. These results provide corroboration for a conformational equilibrium underlying allosteric regulation of SHP2, provide powerful tools for characterizing and controlling SHP2 functions, and inform drug discovery against SHP2.

59 BASIC BIOLOGICAL SCIENCES↗