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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 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Glassy Carbon Substrate Oxidation Effects on Electrode Stability for Oxygen Evolution Reaction Catalysis Stability Benchmarking

Employing benchmarking metrics to capture the activity and stability of electrocatalysts for the oxygen evolution reaction (OER) in acid is a critical practice that enables meaningful comparison of catalyst material candidates reported throughout the literature. In this work, we find that ubiquitously used glassy carbon electrode substrates oxidize under typical OER operating conditions, forming a pacified, electrically insulating, and oxygen-rich surface layer that causes drastic loss of current density over the course of extended chronoamperometric stability tests at an anodic potential of 1.7 VRHE. We show that the experimentally observed stability of glassy carbon-based electrodes is approximately two orders of magnitude lower than that expected solely from dissolution-based catalyst intrinsic stability of Ir-based catalysts. We additionally find that glassy carbon-based electrode stability measured by chronoamperometric holds is greatly impacted by catalyst loading, with high catalyst loadings improving the stability of the overall electrode via a protective effect on the glassy carbon substrate. Altogether, our investigation highlights that glassy carbon is not electrochemically inert under OER conditions on the timescale of common stability tests, which can cause electrodes to exhibit performance losses that do not reflect the intrinsic stability of the actual catalyst material being investigated. In light of our findings, we underscore the usefulness of metrics, such as the S-number, to reflect intrinsic catalyst material stability.

25 ENERGY STORAGE↗
DOE OSTI2016

Supported Tetrahedral Oxo-Sn Catalyst: Single Site, Two Modes of Catalysis

We reported mild calcination in ozone of a (POSS)-Sn- (POSS) complex grafted on silica generated a heterogenized catalyst that mostly retained the tetrahedral coordination of its homogeneous precursor, as evidenced by spectroscopic characterizations using EXAFS, NMR, UV–vis, and DRIFT. The Sn centers are accessible and uniform and can be quantified by stoichiometric pyridine poisoning. This Sn-catalyst is active in hydride transfer reactions as a typical solid Lewis acid. However, the Sn centers can also create Brønsted acidity with alcohol by binding the alcohol strongly as alkoxide and transferring the hydroxyl H to the neighboring Sn–O–Si bond. The resulting acidic silanol is active in epoxide ring opening and acetalization reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Overcoming ammonia synthesis scaling relations with plasma-enabled catalysis

Correlations between the energies of elementary steps limit the rates of thermally catalysed reactions at surfaces. Here, we show how these limitations can be circumvented in ammonia synthesis by coupling catalysts to a non-thermal plasma. We postulate that plasma-induced vibrational excitations in N 2 decrease dissociation barriers without influencing subsequent reaction steps. We develop a density-functional-theory-based microkinetic model to incorporate this effect, and parameterize the model using N 2 vibrational excitations observed in a dielectric-barrier-discharge plasma. We predict plasma enhancement to be particularly great on metals that bind nitrogen too weakly to be active thermally. Ammonia synthesis rates observed in a dielectric-barrier-discharge plasma reactor are consistent with predicted enhancements and predicted changes in the optimal metal catalyst. The results provide guidance for optimizing catalysts for application with plasmas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Reactivity descriptors in acid catalysis: acid strength, proton affinity and host–guest interactions

Brønsted acids mediate chemical transformations via proton transfer to bound species and interactions between the conjugate anion and bound cationic intermediates and transition states that are also stabilized by van der Waals forces within voids of molecular dimensions in inorganic hosts. This Feature Article describes the relevant descriptors of reactivity in terms of the properties of acids and molecules that determine their ability to donate and accept protons and to reorganize their respective charges to optimize their interactions at bound states. The deprotonation energy (DPE) of the acids and the protonation energy (Eprot) of the gaseous analogs of bound intermediates and transition states reflect their respective properties as species present at non-interacting distances. These properties accurately describe the reactivity of acids of a given type, such as polyoxometalates (POM) with a given type of addenda atom but different central atoms and heterosilicates, for different families of reactions. They do not fully capture, however, differences among acid types (e.g., Mo and W POM, heterosilicates, mineral acids) for diverse types of chemical transformations (e.g., elimination, isomerization, dimerization, condensation). The incompleteness of such descriptors reflects their inability to describe how protonated molecular species and conjugate anions restructure their respective charges when present as a binding pair at interacting distances. Such interaction energies represent electrostatic forces that depend on charge distributions in the cations and anions and the ability to reorganize the distributions to maximize the interactions. In the case of deprotonation, the electrostatic and charge reorganization components of DPE for various acids solely reflect the ability of the conjugate anion to accept and distribute the negative charge, a characteristic unique of each type of solid acid and specifically of the composition of its extended conjugate anion framework. The energy required to accept and rearrange the positive charge in bound intermediates and transition states reflects, in turn, their respective ability to recover the ionic and covalent components of DPE, the energy required to detach proton from conjugate anions. The DPE components and the recovery fractions together lead to a modified DPE, which captures only the part of DPE that remains unrecovered by the ion-pair interactions at bound intermediates and transition states, as the unifying descriptor for broad families of acids and reactions. The electrostatic and charge reorganization energies involved in these general descriptors are placed in historical context by assessing their connections to the heuristics of hard–soft acid–base displacements. Further development of these concepts requires benchmarking and extension of electrostatic and reorganization components of energies for a more diverse set of reaction types and acid families and advancement of methods for more efficient calculations of electrostatic interactions. Reactivity descriptors must also account for dispersive interactions between host cavities and guest molecules, requiring a framework analogous to the one described here for ion-pair interactions; these dispersive interactions depend on the fit between their shapes and sizes as well as their ‘‘structural stiffness’’ that determines the ability to modify the shapes of molecules and voids to minimize free energy. Entropy considerations and estimates of their dependence on properties of catalysts and molecules are also required for accurately determining Gibbs free energies that ultimately determine reaction rates.

Deshlahra, Prashant↗
DOE OSTI2015

Human γ-glutamyl transpeptidase 1: Structures of the free enzyme, inhibitor-bound tetrahedral transition states, and glutamate-bound enzyme reveal novel movement within the active site during catalysis [Human gamma-glutamyl transpeptidase: Inhibitor binding and movement within the active site]

γ-Glutamyl transpeptidase 1 (GGT1) is a cell surface, N-terminal nucleophile hydrolase that cleaves glutathione and other γ-glutamyl compounds. GGT1 expression is essential in cysteine homeostasis, and its induction has been implicated in the pathology of asthma, reperfusion injury, and cancer. In this study, we report four new crystal structures of human GGT1 (hGGT1) that show conformational changes within the active site as the enzyme progresses from the free enzyme to inhibitor-bound tetrahedral transition states and finally to the glutamate-bound structure prior to the release of this final product of the reaction. The structure of the apoenzyme shows flexibility within the active site. The serine-borate-bound hGGT1 crystal structure demonstrates that serine-borate occupies the active site of the enzyme, resulting in an enzyme-inhibitor complex that replicates the enzyme's tetrahedral intermediate/transition state. The structure of GGsTop-bound hGGT1 reveals its interactions with the enzyme and why neutral phosphonate diesters are more potent inhibitors than monoanionic phosphonates. These structures are the first structures for any eukaryotic GGT that include a molecule in the active site covalently bound to the catalytic Thr-381. The glutamate-bound structure shows the conformation of the enzyme prior to release of the final product and reveals novel information regarding the displacement of the main chain atoms that form the oxyanion hole and movement of the lid loop region when the active site is occupied. Lastly,tThese data provide new insights into the mechanism of hGGT1-catalyzed reactions and will be invaluable in the development of new classes of hGGT1 inhibitors for therapeutic use.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Fabrication of Carbon-Platinum Interdigitated Array Electrodes and Their Application for Investigating Homogeneous Hydrogen Evolution Catalysis

Interdigitated array electrodes (IDAEs) with one carbon electrode and the other platinum electrode were constructed by electrodepositing platinum on one set of the carbon electrodes. Platinum deposition was confirmed by scanning electron microscope (SEM) and cyclic voltammetry. The width of the carbon and platinum digits is less than 2 μm and the gap between two adjacent digits is around 3 μm. The carbon-platinum IDAEs benefit from the characteristics of both carbon and platinum in that carbon can provide a wide nonreactive potential window while platinum is a good catalyst for hydrogen reactions making it useful to characterize the catalytic hydrogen production cycle of the molecular electrocatalyst [Ni(P Ph 2 N Ph 2 ) 2 (CH 3 CN)](BF 4 ) 2 (where P Ph 2 N Ph 2 is 1,3,5,7-tetraphenyl-1,5-diaza-3,7-diphosphacyclooctane). With properly set potentials, the molecular electrocatalyst was reduced at the carbon digits to initiate a homogeneous H 2 production reaction while the platinum digits detect the H 2 by oxidation, providing direct evidence of its production rate from the catalytic cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Quantum Theory of Semiconductor Photo-Catalysis and Solar Water Splitting / Theory and Computation for Semiconductor Catalysis of Solar Water Splitting / Static and Dynamic Thermal Effects in Solids. Final Report

This is the final report. The finished research was published in 27 journal papers listed below. The topics fall roughly into seven categories: Photochemistry of water at the GaN ($10\bar{1}0$) surface; Quasiparticles: Band electrons and Anharmonic phonons; Quasiharmonic theory; Anharmonic lattice thermal conductivity; Water and Ice; Electron-phonon effects; and, Alloy theory.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Workshop on Addressing Rigor and Reproducibility in Thermal, Heterogeneous Catalysis

Heterogeneous catalysis has long served as the bedrock of the manufacturing of energy carriers, fuels and chemicals, and various technologies for pollution abatement. The significant complexity and variability spanning the entire breadth of catalyst material properties, synthesis methods, characterization techniques, and evaluation procedures, has focused attention on the need to establish community-accepted best practices for ensuring high-quality, benchmarked, and reproducible data. In addition, increased societal urgency to transition to clean energy and reduce greenhouse gas concentrations has incentivized interdisciplinary, convergent, and translational approaches to catalysis research in recent years. Research engineers and scientists with expertise cutting broadly across materials science, chemical synthesis, interfacial science, spectroscopy, and methods of data science and computational simulation, all bring diverse and important perspectives to catalysis research, but often with little awareness of the complexity of catalytic systems, especially in their working environment. As has already occurred in other scientific fields, there has been growing recognition and consensus in the heterogeneous catalysis research community that mechanisms are needed to improve the rigor and reproducibility (R&R) of experimental measurements, to ensure alignment of the broader research community with a common core of best practices specific to the realization of high-quality catalysis research. Similarly, the field is moving rapidly toward computationally informed and data science-driven catalyst design, but the success of implementing such predictive tools hinges on model training and validation rooted in rigorously obtained and reproducible experimental data that are benchmarked to common specifications. As such, this workshop was convened to prepare a report summarizing best practices for reporting data and performing experiments that researchers can use to benchmark, validate, and reproduce data in specific sub-fields of thermal, heterogeneous catalysis. Additionally, we discussed recommendations for future actions that may improve R&R in this field. The workshop organizers and participants include a diverse range of catalysis researchers from various employment sectors (e.g., academia, industry, national laboratory), institutional mission and resources (e.g., PhD-granting research universities, non-PhD-granting teaching universities), career stage (e.g., early, mid and late-career), technical expertise, and demographic background. This diverse group was involved in the discussion of workshop agenda items, writing this report, and discussing possible future action items for the community to consider, which helped ensure that a broad range of perspectives were captured in the description of the problems at hand and the creation of actionable solutions that may be effectively adopted by the diverse practitioners in catalysis research. Importantly, this group of workshop participants also included very early career researchers (e.g., senior PhD students, postdoctoral scholars) who will become the next generation of scientific leaders in various sectors, thus capturing emerging perspectives of newcomers to the field to shape its future while positively impacting the development of its future workforce. We envision that this effort will help advance the field of catalysis science by improving the rigor and reproducibility of experimental data collected by current researchers and future newcomers to the field, which is of broad importance to health and vitality of any scientific discipline. Therefore, best practices identified in this endeavor for thermal heterogeneous catalysis can be translated to such efforts in other areas of catalysis and other scientific fields involving the study of materials, and vice versa. We also envision this to be an ongoing effort, with future workshops that are convened to discuss issues of rigor and reproducibility on technical topics that were unable to be covered in this workshop due to its scope limitations, and as emerging methods and materials become more prevalent in the research community.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Support for U.S. Participants at the 18 th International Congress on Catalysis

The 18 th International Congress on Catalysis (ICC) was held Lyon, France on July 14-19, 2024. It provided a premier technical gathering in surface and organometallic catalysis, industrial homogeneous and heterogeneous catalysis, electrocatalysis, photocatalysis, and catalysis in condensed media. This meeting brough together participants from academia, industry, and national laboratories. The organization that overseed this meeting was the Council of the International Congress on Catalysis. This international committee has over 27 signature countries. The United States is represented in the Council of the International Congress on Catalysis through two permanent representatives. These representatives are elected by the Board of Directors of the North American Catalysis Society (NACS), an organization which coordinates and overseas the activities of 12 largely autonomous clubs within the United States, Canada, and Mexico. The critical importance of catalysis is reflected by the fact that 25-30% of all manufactured goods in the United States involve at least one catalytic step. Because advances in a large number of catalytic processes, which are crucial to U.S. interests, were presented at this meeting, it was important to ensure participation from both the U.S. academic and the industrial sectors.

02 PETROLEUM↗
DOE OSTI2021

Heterogeneous Diels–Alder tandem catalysis for converting cellulose and polyethylene into BTX

Producing biomass-derived aromatic hydrocarbons via controllable Diels–Alder reactions is a promising approach to recover energy and chemicals from waste streams. A tandem Diels–Alder catalysis consisting of SAPO-34 and Fe/HZSM-5 (stacked catalysis or mixed catalysis) was evaluated for thermochemical conversion of cellulose and polyethylene blends into benzene, toluene, and xylenes (BTX). Aromatization catalyst type significantly affected the activity of tandem catalysis, and the BTX obtained from the HZSM-5 stacked catalysis was ~2.3 times higher than that of the USY stacked one. An introduction of Fe active promoters into HZSM-5 increased the Lewis to Brønsted acid sites molar ratio (L/B) from 0.4 to 4.1. The comparison between Fe/HZSM-5 stacked catalysis and parent HZSM-5 single catalysis indicated that the former was more effective for BTX production, obtaining a nearly two-fold increase in yield with a high selectivity of 82.8%. A close proximity between Fe/HZSM-5 and SAPO-34 in the mixed catalysis increased the BTX enhancement to 1.8. A synergistic effect was provided by the coordination of Lewis and Brønsted acid sites in the Fe/HZSM-5 mixed catalysts for facilitating BTX generation, achieving a maximum of 25.9% at a Fe/HZSM-5 to SAPO-34 mass ratio of 1:1 with a theoretical L/B of 7.2. Finally, this work provides a sustainable strategy to produce biomass-derived aromatic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗