Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “REACTIVITY”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 703 records · Page 39
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

Abstract Faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.7) undergo mild dealumination at moderate ion exchange conditions (0.01 to 0.6 M of NH 4 NO 3 solutions) resulting in protons circumscribed by sodalite cages becoming accessible for reaction without conspicuous changes to bulk crystallinity. The ratio of protons in sodalite cages (H SOD ) to supercages (H SUP ) can be systematically manipulated from 0 to ca. 1 by adjusting ammonium concentrations used in ion exchange. The fraction of accessible protons in the sodalite cages is assessed by virtue of infrared spectra for H‐D exchange of deuterated propane based on the band area ratio of OD 2620 /OD 2680 (OD SOD /OD SUP ). Protons in sodalite cages (H SOD ) show higher rate constants of propane dehydrogenation ( k D ) and cracking ( k C ) than protons in supercages (H SUP ) plausibly due to confinement effects being more prominent in smaller voids. Rate constants of dehydrogenation and cracking including k D / k C ratios are also augmented as the fraction of accessible protons in the sodalite cages is enhanced. These effects of accessibility and reactivity of protons in sodalite cages hitherto inconspicuous are revealed herein via methods that systematically increase accessibility of cations located in sodalite cages.

Li, Xinyu↗
DOE OSTI2023

Hydrogen Evolution on Electrode‐Supported Pt n Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity

Abstract We report the size‐dependent activity and stability of supported Pt 1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with size‐dependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (≈2 H/Pt). An ensemble‐based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. The stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential‐ and adsorbate‐coverage‐dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.

Zhang, Zisheng↗
DOE OSTI2023

High‐Spin and Reactive Fe 13 Cluster with Exposed Metal Sites

Abstract Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp* 4 W 4 Fe 13 S 12 , displaying a Fe 13 core with M−M bonds that has precedent only in main group and late metal chemistry. M 13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp* 4 W 4 Fe 13 S 12 displays a large spin ground state of S =13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

Scott, Anna G.↗
DOE OSTI2021

Prediction of Reactive Nitrous Acid Formation in Rare‐Earth MOFs via ab initio Molecular Dynamics

Abstract Reactive gas formation in pores of metal–organic frameworks (MOFs) is a known mechanism of framework destruction; understanding those mechanisms for future durability design is key to next generation adsorbents. Herein, an extensive set of ab initio molecular dynamics (AIMD) simulations are used for the first time to predict competitive adsorption of mixed acid gases (NO 2 and H 2 O) and the in‐pore reaction mechanisms for a series of rare earth (RE)‐DOBDC MOFs. Spontaneous formation of nitrous acid (HONO) is identified as a result of deprotonation of the MOF organic linker, DOBDC. The unique DOBDC coordination to the metal clusters allows for proton transfer from the linker to the NO 2 without the presence of H 2 O and may be a factor in DOBDC MOF durability. This is a previously unreported mechanisms of HONO formation in MOFs. With the presented methodology, prediction of future gas interactions in new nanoporous materials can be achieved.

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

Enhanced Reactivity of Accessible Protons in Sodalite Cages of Faujasite Zeolite

We report Faujasite (FAU) zeolites (with Si/Al ratio of ca. 1.7) undergo mild dealumination at moderate ion exchange conditions (0.01 to 0.6 M of NH 4 NO 3 solutions) resulting in protons circumscribed by sodalite cages becoming accessible for reaction without conspicuous changes to bulk crystallinity. The ratio of protons in sodalite cages (H SOD ) to supercages (H SUP ) can be systematically manipulated from 0 to ca. 1 by adjusting ammonium concentrations used in ion exchange. The fraction of accessible protons in the sodalite cages is assessed by virtue of infrared spectra for H-D exchange of deuterated propane based on the band area ratio of OD 2620 /OD 2680 (OD SOD /OD SUP ). Protons in sodalite cages (H- SOD ) show higher rate constants of propane dehydrogenation (k D ) and cracking (k C ) than protons in supercages (H SUP ) plausibly due to confinement effects being more prominent in smaller voids. Rate constants of dehydrogenation and cracking including k D /k C ratios are also augmented as the fraction of accessible protons in the sodalite cages is enhanced. These effects of accessibility and reactivity of protons in sodalite cages hitherto inconspicuous are revealed herein via methods that systematically increase accessibility of cations located in sodalite cages.

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

Reactivities of Interstitial Hydrides in a Cu 11 Template: En Route to Bimetallic Clusters

In sharp contrast to surface hydrides, reactivities of interstitial hydrides are difficult to explore. When treated with a metal ion (Cu + , Ag + , and Au + ), the stable CuI dihydride template [Cu 11 H 2 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] (H 2 Cu 11 ) generates surprisingly three very different compounds, namely [CuH 2 Cu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 ] + (1), [AgH 2 Cu 14 {S 2 P(OiPr) 2 } 6 ((C≡CPh) 6 ] + (2), and [AuCu 11 {S 2 P(OiPr) 2 } 6 (C≡CPh) 3 Cl] (3). Compounds 1 and 2 are both MI species and maintain the same number of hydride ligands as their H 2 Cu 11 precursor. Neutron diffraction revealed the first time a trigonal-pyramidal hydride coordination mode in the AgCu 3 environment of 2. 3 has no hydride and exhibits a mixed-valent [AuCu 11 ] 10+ metal core, making it a two-electron superatom.

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

Hydrogen Evolution on Electrode–Supported Ptn Clusters: Ensemble of Hydride States Governs the Size Dependent Reactivity

We report the size-dependent activity and stability of supported Pt1,4,7,8 for electrocatalytic hydrogen evolution reaction, and show that clusters outperform polycrystalline Pt in activity, with sizedependent stability. To understand the size effects, we use DFT calculations to study the structural fluxionality under varying potentials. We show that the clusters can reshape under H coverage and populate an ensemble of states with diverse stoichiometry, structure, and thus reactivity. Both experiment and theory suggest that electrocatalytic species are hydridic states of the clusters (~2 H/Pt). An ensemble-based kinetic model reproduces the experimental activity trend and reveals the role of metastable states. Furthermore, the stability trend is rationalized by chemical bonding analysis. Our joint study demonstrates the potential- and adsorbate-coverage-dependent fluxionality of subnano clusters of different sizes and offers a systematic modeling strategy to tackle the complexities.

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

High-Spin and Reactive Fe 13 Cluster with Exposed Metal Sites

We report atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp* 4 W 4 Fe 13 S 12 , displaying a Fe 13 core with M-M bonds that has precedent only in main group and late metal chemistry. M 13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp* 4 W 4 Fe 13 S 12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.

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

​Genuine Carbene Versus Carbene–Like Reactivity

Singlet carbenes are not always isolable and often even elude direct detection. When they escape observation, their formation can sometimes be evidenced by in-situ trapping experiments. Furthermore, is carbene-like reactivity genuine evidence of carbene formation? Herein, using the first example of a spectroscopically characterized cyclic (amino)(aryl)carbene (CAArC), we cast doubt on the most common carbene trapping reactions as sufficient proof of carbene formation.

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

ReaxFF reactive force field model enables accurate prediction of physiochemical and mechanical properties of crystalline and amorphous shape‐memory polyurethane

Abstract We investigate reactive force field (ReaxFF) prediction of physiochemical and mechanical properties, and stimuli response behavior of a shape‐memory polyurethane (SMPU) rigid segment. We used SMPUs as a platform to link the rigid/hard segment domain crystallinity with properties that can also be experimentally measured. Specifically, we developed models for crystalline and amorphous forms of a common rigid segment of SMPUs, for example, 4,4′‐diphenylmethane diisocyanate (MDI) with n‐butanediol (BDO), denoted as MDI‐BDO. ReaxFF molecular dynamics simulations with equilibrium dynamics are performed by controlling mass, temperature, and pressure or volume to predict the structural and physiochemical properties of crystalline and amorphous rigid segments of SMPU systems, followed by simulating their XRD and FTIR patterns, respectively. Non‐equilibrium ReaxFF simulations are implemented by using uniaxial box deformation technique to study response‐behavior of crystalline SMPU under tensile loading and during stress‐relaxation. The model and simulation scheme presented in this study demonstrates a robust theoretical pathway toward application‐dictated, on‐demand design of high‐performance SMPUs in applications such as soft robotics.

Afroz, Mohammad M.↗
DOE OSTI2022

Consequences of Intrapore Liquids on Reactivity, Selectivity, and Stability for Aldol Condensation Reactions on Anatase TiO 2 Catalysts

Abstract This study provides evidence and mechanistic interpretations for the significant consequences of intrapore non‐polar liquids on acetone aldol condensation turnover rates, selectivity to primary dimer products, and catalyst stability for reactions at Lewis acid‐base site pairs on TiO 2 surfaces. These non‐polar liquids confer such benefits through the preferential stabilization of transition states (TS) for adsorption (“entry”) and desorption (“exit”) steps, which place their respective reactants or products within a solvating outer sphere environment. The extent to which non‐polar fluids ( n ‐heptane) form an intrapore liquid phase within TiO 2 voids was obtained from N 2 uptakes using established formalisms that consider the different molal volume, surface tension, and volatility between N 2 and n ‐heptane. Acetone condensation rates are limited by C−H activation, an “entry” step that forms bound prop‐1‐en‐2‐olates via a TS stabilized by intrapore liquids, leading to higher aldol condensation turnover rates as n ‐heptane pressure increases and active TiO 2 surfaces become increasingly immersed within a non‐polar liquid phase. These liquids solvate the late TS structures that mediate the desorption of primary C 6 condensation products even more effectively than those involved in prop‐1‐en‐2‐olate formation or in nucleophilic attack events that later form C−C bonds. Such preferential solvation favors desorption over C−C coupling events, thus disfavoring the formation of larger oligomers that become stranded at active sites, thus leading to much slower deactivation. Moreover, solvation by non‐polar liquids also leads to C 6 alkanones as the sole products formed in a single surface sojourn. These effects of a non‐polar dense phase circumvent the inherent stability, reactivity, and selectivity hurdles that have precluded practical aldol condensation catalysis on Lewis acid‐base pairs at oxide surfaces; these consequences are demonstrated here for TiO 2 catalysts, acetone aldol condensation reactions, and n ‐heptane as the non‐polar liquid but through strategies, concepts, and mechanistic features that extend to other systems. More generally, these observations and their mechanistic origins demonstrate how a contacting liquid preferentially solvates TS structures for elementary steps that involve either reactants arriving from or products entering into an outer sphere environment that contains a dense non‐polar phase.

Kadam, Shashikant A.↗
DOE OSTI2024

PCET‐Driven Reactivity of Neptunyl(VI) Yields Oxo‐Bridged Np(V) and Np(IV) Species

Two unconventional polynuclear complexes of neptunium (Np) featuring mono-mathematical equation -oxo motifs have been accessed by proton-coupled electron transfer (PCET) reactivity involving the dissolution of neptunyl(VI) diacetate dihydrate (NpO 2 (OAc) 2 (H 2 O) 2 ∙ HOAc) in methanol followed by addition of a pentadentate Schiff-base ligand. One complex is a mixed-valent [Np V ,Np IV , Np V ] trimer with two bridging mathematical equation μ 2 -oxos and the other is a [Np V , Np V ] dimer featuring a single mathematical equation μ 2 -oxo. In both complexes the outer Np centers are capped with terminal oxo ligands. Spectroscopic and spectrokinetic studies aimed at elucidating mechanistic details of complex formation in this system show that intermediate multinuclear [Np V O 2 (OAc)] n species form prior to metal chelation by the ligand; electrolysis experiments demonstrate that production of Np(V) gives rise to asynchronous proton transfer that does not occur otherwise (in the Np(VI) state) as well as condensation with loss of H 2 O and formation of the polynuclear complexes. We attribute the oxo-deficient nature of these products, with respect to conventional actinyl ([AnO 2 ] m+ ) species, to the reduction/condensation reaction sequence of PCET.

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

Large-scale reactive thermoset printing: Complex interactions between temperature evolution, viscosity, and cure shrinkage

Thermoset composites are strong candidates for large-scale material extrusion additive manufacturing (AM). However, uncured thermoset composites become unstable as print height increases. Here, chemical initiation of vinyl ester immediately before deposition was used to suppress collapse and enable large-scale thermoset printing. Structural stability was assessed by printing thin walls at various layer times and monitoring thermal gradients with an infrared camera. Stable printing was observed at a layer time of 4.50 min, approximately half the gel time of the material (8 min). Self-weight collapse occurred at short layer time (0.68 min), whereas warpage occurred at long layer time (6.50 min). Here, a new behavior was discovered at intermediate layer time (2.25 min) where the heat generated by the reaction causes new, un-gelled layers to flow. Forced convection eliminates this behavior, stabilizing the 2.25-min layer time print. These findings motivated development of a less exothermic material system, which was used to print a large-scale mold and demonstrate the value of this understanding. By presenting these challenges of large-scale reactive thermoset AM for the first time, this work motivates focused studies of the complex interplay between rheological, thermal, and chemical behaviors to improve the feasibility of large-scale thermoset AM. Tensile properties of the printed material were also measured. Longitudinal and transverse elastic moduli are 3.79 and 2.95 GPa, respectively, and corresponding tensile strengths are 36.11 and 18.83 MPa. The glass transition temperature is 93.13 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2023

High-temperature active oxidation of nanocrystalline silicon-carbide: A reactive force-field molecular dynamics study

Flexible woven SiC ceramics are prone to accelerated fiber embrittlement under high temperature oxidation in dynamic oxygen environments. The nanocrystalline structure of the constituent fibers impacts the reaction kinetics and phase transformations during active oxidation. However, fundamental understanding and quantification of grain boundary effects on oxidation behavior in nanocrystalline SiC remain elusive when temperatures exceed 1500 K. This study deploys large-scale molecular dynamics simulations with a reactive force-field to elucidate the complex roles of atomic oxygen reservoir conditions and grain size on oxidation kinetics and the nature of oxides produced in both monocrystalline and nanocrystalline 3C-SiC between 1100 K and 2000 K. The simulations with dynamically replenished oxygen provide good agreement with oxidation kinetics and activation energies for the monocrystalline Si(100) and C(100) orientations published in the available literature. This study reveals that, by contrast, nanocrystalline SiC samples exhibit two distinct oxidation kinetics with a transition point at 1500 K due to surface melting, which is supported by experimental evidence. The introduction of a grain-boundary network produces a two-fold decrease in oxidation activation energies compared to monocrystalline SiC below 1500 K. Above 1500 K, however, the activation energies rise substantially due to the formation of a liquid Si phase at the SiC/Si oxide interface. Further, it is shown that the stability of the interfacial liquid phase is promoted by incoherent grain boundaries in the crystalline SiC. These findings are important for the deployment of nanocrystalline SiC fibers in advanced thermal protection systems for high-temperature applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Numerical investigations to identify environmental factors for field-scale reactive transport of pathogens at riverbank filtration sites

While induced bank filtration is a proven method for facilitating sustainable drinking water production, it is at risk from surface water contaminations (e.g., pathogens). Induced bank filtration and pathogen transport in groundwater have been studied extensively. However, long-term studies that consider real-world conditions are missing. These conditions include seasonal changes to environmental conditions and waterworks operations. Therefore, to analyze the effect of seasonal changes on the transport of human pathogenic viruses and their indicators in induced bank filtration, concentrations of adenoviruses and pathogen indicators were monitored over 16 months at an active bank filtration plant at the Rhine River, in Düsseldorf (Germany). Based on this data, a 2D groundwater model was created in PFLOTRAN that simulated flow, heat transport, conservative transport of chloride and the resulting electrical conductivity, reactive transport of oxygen and nitrate, and colloid-based transport of coliforms, somatic coliphages, and adenoviruses. The results show that reduced travel time was the key factor determining periods with a low removal of coliforms and somatic coliphages in the aquifer. Travel time was controlled by river level variations during rainy seasons, and the waterworks extraction rates during dry seasons. Further, for adenovirus transport, travel distance in the subsurface appeared to be the key factor, while travel time had no significant impact. Coliform removal increased when the colmation layer permeability decreased, while coliphage and adenovirus removal was unaffected by the colmation layer permeability. Seasonal changes in temperature and oxygen content did not significantly impact the removal of coliphages and adenoviruses in groundwater. Denitrifying conditions correlated with a lowered coliform removal, but the modelling could not establish a connection between denitrifying conditions and coliform removal. Our study showed that removal of pathogens and pathogen indicators at induced bank filtration plants varies greatly in time and space (e.g., for coliforms from 1 to 4 log-levels at 20m travel distance), and that adenovirus transport differs considerably from transport of coliforms and somatic coliphages.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Razorback – A reactor transient analysis code for large rapid reactivity additions in a natural circulation research reactor

Research reactors play an important role in higher education, scientific research, and medical radioisotope production around the world. It is thus important to ensure the safety of facility workers and the public. This work presents a new reactor transient analysis code referred to as Razorback. The code has been developed for the evaluation of large rapid reactivity addition in research reactors. Its initial focus is the Annular Core Research Reactor (ACRR) at Sandia National Laboratories. Results have been validated against ACRR pulse operations. Razorback models the reactor kinetics, fuel element heat transfer, fuel element thermal expansion, and natural circulation coolant channel thermal-hydraulic response. Simulation results for ACRR pulse operations are shown to agree very well with operational data obtained from the ACRR. Finally, Razorback is expected to be a valuable tool for ACRR pulse performance prediction and ACRR reactor safety analyses.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

SCALE inventory and reactivity analysis as part of the Hermes 2021 PSAR review

The readiness of SCALE for comprehensive studies of pebble-bed reactors has been demonstrated through detailed analysis of a fluoride salt–cooled, high-temperature pebble-bed reactor (PB-FHR). The methods developed for pebble-bed reactor modeling in SCALE, particularly for inventory generation, have proven effective in gaining insights into the reactor physics of this advanced reactor. Excellent agreement with another code package has been observed, further highlighting SCALE’s strong performance. The SCALE results supported the US Nuclear Regulatory Commission’s construction permit application review of the Hermes low-power PB-FHR demonstration reactor. A SCALE model of the Hermes reactor was developed at Oak Ridge National Laboratory using information from the Preliminary Safety Analysis Report (PSAR) and supplemented with publicly available data. SCALE reactivity coefficient simulations reproduced PSAR results within 1σ statistical uncertainties. Sensitivity studies emphasized the importance of graphite specifications for accurate keff predictions.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Site-specific surface reactivity on SnO 2 : Evaluating selective atomic layer deposition processes

Area selective atomic layer deposition (AS-ALD) is a bottom-up synthesis approach with potential for deposition with molecular level precision. Here, the site-specific hydration of metal oxide substrates, combined with surface H 2 O-selective ALD processes, provides a potentially powerful path to targeted synthesis. Density functional theory (DFT) calculations are used to predict the thermodynamics of ALD precursor reactivity and hydration for (001), (101), (110), and (100) rutile SnO 2 facets as a function of temperature. Trimethylaluminum (TMA) and dimethyl aluminum isopropoxide (DMAI) dimers are predicted to react with both dehydrated and hydrated SnO 2 (001), (101), and (110) facets at ALD-relevant temperatures, while the SnO 2 (100) facet is predicted to be uniquely unreactive with TMA and DMAI monomers as well as dehydrate near 177 °C making this facet more amenable to targeted ALD. In situ ellipsometric studies of Al 2 O 3 ALD on polycrystalline SnO 2 at 150 °C are consistent with the computational predictions of rapid and unselective nucleation, in stark contrast to inhibited and selective ALD on isostructural rutile TiO 2 .

Atomic Layer Deposition↗