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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Mechanisms and site requirements for NO and NH 3 oxidation on Cu/SSZ-13

Two series of Cu/SSZ-13 catalysts were synthesized via aqueous solution and solid-state ion exchange using SSZ-13 supports of varying Si/Al ratios. The isolated and multinuclear Cu content of these catalysts were determined by H 2 temperature programmed reduction (H 2 -TPR). Multinuclear Cu in these catalysts, including in situ Cu- dimers formed from ZCu II OH coupling and permanent CuO clusters, are active species for dry NO oxidation. NH 3 oxidation on these catalysts follows an internal SCR (i-SCR) mechanism, i.e., a portion of NH 3 is first oxidized to NO, then NO is selectively reduced by the remaining NH 3 to N 2 . NH 3 oxidation displays distinct kinetic behavior below ~300 °C and above ~400 °C. At low temperature the results indicate that NH 3 -solvated mobile Cu-ions are the active centers. CuO clusters, when present, also contribute to the low temperature activity by catalyzing NH 3 oxidation to NO. At high temperature, in situ Cu-dimers and CuO clusters catalyze NH 3 oxidation to NO, and isolated Cu-ions catalyze SCR to realize the cascade turnovers. For both NO and NH 3 oxidation, Cu-dimers balanced by framework charges of close proximity appear to be more active than Cu-dimers balanced by distant framework charges. However, the former Cu-dimers are less stable than the latter and tend to split into monomers in the presence of vicinal Brønsted acid sites. Via density functional theory (DFT) calculations, the i-SCR mechanism for low temperature NH 3 oxidation, i.e., the energetic favorability for the involvement of the NO intermediate, is justified. Furthermore, the DFT results also agree with experimental data that the formation of Cu-dimers from ZCu II OH dimerization is essential for NH 3 oxidation at high temperature.

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

Catalytic Bias in Enzymatic Metal Cofactor-Based Oxidation-Reduction Catalysis

Catalytic bias refers to the relative rate preference of a catalyst for either the forward or reverse direction. In enzymatic metal cofactor-based oxidation-reduction catalysis, the tuning of catalytic bias plays an underlying role in controlling rates of reactivity. For this, enzymes have evolved complex active sites that can exist in multiple oxidation states with differing reduction potentials in order to achieve challenging multi-step, oxidation-reduction reactions. Conceivably, the relative stability of the intermediates that contribute to determining the rate-limiting step of the catalytic cycle could impose catalytic bias, although mechanisms for this concept are just beginning to be realized. As one example, recent work on Clostridium pasteurianum [FeFe]-hydrogenases which catalyze reversible hydrogen oxidation have shown that the differential stabilization/destabilization of active site oxidation states through either static or dynamic protein interactions can preferentially promote either the hydrogen oxidation or proton reduction direction of the reaction. This revealed how an enzymatic cofactor can impose bias in oxidation-reduction catalysis through various tuning mechanisms by protein scaffold interactions. The hypothesis based on achieving catalytic bias through the modulation of cofactor oxidation states critical for the reaction cycle can be extended more generally to other cofactor-based oxidation-reductions catalysts. The current understanding of catalytic bias has significant implications for the design of synthetic catalysts used in industrial settings, as well as providing a greater fundamental understanding of the factors that control metabolic processes in all life.

catalysis↗
DOE OSTI2020

Oxygen evolution reaction over catalytic single-site Co in a well-defined brookite TiO 2 nanorod surface

Efficient electrocatalysts for the oxygen evolution reaction (OER) are paramount to the development of electrochemical devices for clean energy and fuel conversion. However, the structural complexity of heterogeneous electrocatalysts makes it a great challenge to elucidate the surface catalytic sites and OER mechanisms. Here, we report that catalytic single-site Co in a well-defined brookite TiO 2 nanorod (210) surface (Co-TiO 2 ) presents turnover frequencies that are among the highest for Co-based heterogeneous catalysts reported to date, reaching 6.6 ± 1.2 and 181.4 ± 28 s -1 at 300 and 400 mV overpotentials, respectively. Based on grand canonical quantum mechanics calculations and the single-site Co atomic structure validated by in situ and ex situ spectroscopic probes, we have established a full description of the catalytic reaction kinetics for Co-TiO 2 as a function of applied potential, revealing an adsorbate evolution mechanism for the OER. The computationally predicted Tafel slope and turnover frequencies exhibit exceedingly good agreement with experiment.

25 ENERGY STORAGE↗
DOE OSTI2021

Transition Path Sampling Study of the Feruloyl Esterase Mechanism

Serine hydrolases cleave peptide and ester bonds and are ubiquitous in nature, with applications in biotechnology, in materials, and as drug targets. The serine hydrolase two-step mechanism employs a serine–histidine–aspartate/glutamate catalytic triad, where the histidine residue acts as a base to activate poor nucleophiles (a serine residue or a water molecule) and as an acid to allow the dissociation of poor leaving groups. This mechanism has been the subject of debate regarding how histidine shuttles the proton from the nucleophile to the leaving group. To elucidate the reaction mechanism of serine hydrolases, we employ quantum mechanics/molecular mechanics-based transition path sampling to obtain the reaction coordinate using the Aspergillus niger feruloyl esterase A (AnFaeA) as a model enzyme. The optimal reaction coordinates include terms involving nucleophilic attack on the carbonyl carbon and proton transfer to, and dissociation of, the leaving group. During the reaction, the histidine residue undergoes a reorientation on the time scale of hundreds of femtoseconds that supports the “moving histidine” mechanism, thus calling into question the “ring flip” mechanism. We find a concerted mechanism, where the transition state coincides with the tetrahedral intermediate with the histidine residue pointed between the nucleophile and the leaving group. Moreover, motions of the catalytic aspartate toward the histidine occur concertedly with proton abstraction by the catalytic histidine and help stabilize the transition state, thus partially explaining how serine hydrolases enable poor nucleophiles to attack the substrate carbonyl carbon. Rate calculations indicate that the second step (deacylation) is rate-determining, with a calculated rate constant of 66 s –1 . Altogether, these results reveal the pivotal role of active-site dynamics in the catalytic mechanism of AnFaeA, which is likely similar in other serine hydrolases.

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

Mechanism of Catalysis by L -Asparaginase

Two bacterial type II L -asparaginases, from Escherichia coli and Dickeya chrysanthemi, have played a critical role for more than 40 years as therapeutic agents against juvenile leukemias and lymphomas. Despite a long history of successful pharmacological applications and the apparent simplicity of the catalytic reaction, controversies still exist regarding major steps of the mechanism. In this report, we provide a detailed description of the reaction catalyzed by E. coli type II L -asparaginase (EcAII). Our model was developed on the basis of new structural and biochemical experiments combined with previously published data. The proposed mechanism is supported by quantum chemistry calculations based on density functional theory. In this work, we provide strong evidence that EcAII catalyzes the reaction according to the double-displacement (ping-pong) mechanism, with formation of a covalent intermediate. Several steps of catalysis by EcAII are unique when compared to reactions catalyzed by other known hydrolytic enzymes. Here, the reaction is initiated by a weak nucleophile, threonine, without direct assistance of a general base, although a distant general base is identified. Furthermore, tetrahedral intermediates formed during the catalytic process are stabilized by a never previously described motif. Although the scheme of the catalytic mechanism was developed only on the basis of data obtained from EcAII and its variants, this novel mechanism of enzymatic hydrolysis could potentially apply to most (and possibly all) L -asparaginases.

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

Real-time Atomic-scale Visualization of Reversible Copper Surface Activation during the CO Oxidation Reaction

Dynamic structural and chemical information of catalyst surface during a catalytic reaction is critical for deciphering the mechanisms governing the properties of catalysts. Transition-metal based catalysts have emerged as an important alternative to noble metal catalysts, but their catalytic mechanism remains largely elusive, complicated by dynamic structure and valence evolution. Herein, by using in situ aberration-corrected environmental transmission electron microscopy, we capture, for the first time at atomic level, the dynamic evolution of Cu surface during CO oxidation reaction. We discovered that, under reaction condition, the Cu surface is activated, typically involving 2-3 atomic layers with the formation of a reversible meta-stable phase that only exists during catalytic reactions. Further, we reveal the distinctive role of CO and O2 in the surface activation, featuring CO exposure to lead to surface roughening and consequently formation of low-coordinated Cu atoms, while O2 exposure to induce quasi-crystalline CuOx phase. Corrugated by DFT calculations, we rationalize crystalline CuOx reversibly transforms into the amorphous phase, acting as an active species to facilitate the interaction of gas reactants and catalyzing CO oxidation.

Luo, Langli↗
DOE OSTI2024

Structural characterization of ligand binding and pH-specific enzymatic activity of mouse Acidic Mammalian Chitinase

Chitin is an abundant biopolymer and pathogen-associated molecular pattern that stimulates a host innate immune response. Mammals express chitin-binding and chitin-degrading proteins to remove chitin from the body. One of these proteins, Acidic Mammalian Chitinase (AMCase), is an enzyme known for its ability to function under acidic conditions in the stomach but is also active in tissues with more neutral pHs, such as the lung. Here, we used a combination of biochemical, structural, and computational modeling approaches to examine how the mouse homolog (mAMCase) can act in both acidic and neutral environments. We measured kinetic properties of mAMCase activity across a broad pH range, quantifying its unusual dual activity optima at pH 2 and 7. We also solved high-resolution crystal structures of mAMCase in complex with oligomeric GlcNAcn, the building block of chitin, where we identified extensive conformational ligand heterogeneity. Leveraging these data, we conducted molecular dynamics simulations that suggest how a key catalytic residue could be protonated via distinct mechanisms in each of the two environmental pH ranges. These results integrate structural, biochemical, and computational approaches to deliver a more complete understanding of the catalytic mechanism governing mAMCase activity at different pH. Engineering proteins with tunable pH optima may provide new opportunities to develop improved enzyme variants, including AMCase, for therapeutic purposes in chitin degradation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

Ultrafast Reaction Mechanisms in Multimolecular Ir-Co Catalytic Assemblies for Hydrogen Evolution

Nanosecond optical and X-ray spectroscopy with theoretical calculations reveal formation of a photo-induced distorted tetrahedral CoI intermediate in two Ir/Co multimolecular assemblies and show its protonation as the rate limiting step for H2 photocatalysis. Substitution of the catalysts´ pyridine group on the para position by -COOEt improves the protonation efficiency.

Velascoa, Lucia↗
DOE OSTI2021

Influence of the proton relay spacer on hydrogen electrocatalysis by cobalt hangman porphyrins

A cobalt hangman porphyrin system with a phenyl spacer between the porphyrin ring and an internal carboxylic acid group as well as its non-hangman analogue were synthesized and utilized for the study of the proton-coupled electron transfer (PCET) kinetics attendant to electrocatalytic hydrogen evolution. Cyclic voltammetry (CV) together with simulations show that a short distance between the proton relay and the redox active cobalt center as well as the increased proton donating strength results in superior catalytic activity. Here, the mechanism of hydrogen generation is at the nexus of proton transfer–electron transfer (PTET) and concerted proton–electron transfer (CPET), as opposed to an ETPT mechanism that is characteristic of hangman systems with longer proton relay networks.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1973

An interfaced system for production of methane in a spacecraft

The formose reaction, the homogeneously catalyzed condensation of formaldehyde to sugars, proceeds simultaneously with Cannizzaro and crossed Cannizzaro reactions. Reaction studies in a continuous stirred tank reactor have shown that rate instabilities are exhibited. There are temperature instabilities as well as concentration instabilities in calcium hydroxide catalyst, formaldehyde reactant, and hydroxyl ion. It is postulated that Ca(OH)+ is the actual catalytic species for the formose system. A unifying mechanism is developed that postulates that reactions proceed from a common intermediate complexed species, and that the selectivity for each reaction depends on the nature of the catalyst forming the carbohydrate complex. The catalytic mechanism explains the Lobry de Bruyn-van Eckenstein aldose ketose rearrangements and mutarotations of sugars that also proceed in the system.

Weiss, A. H.↗
DOE OSTI2020

Catalytic upcycling of high-density polyethylene via a processive mechanism

The overconsumption of single-use plastics is creating a global waste catastrophe, with widespread environmental, economic and health-related consequences. In this work we show that the benefits of processive enzyme-catalysed conversions of biomacromolecules can be leveraged to affect the selective hydrogenolysis of high-density polyethylene into a narrow distribution of diesel and lubricant-range alkanes using an ordered, mesoporous shell/active site/core catalyst architecture that incorporates catalytic platinum sites at the base of the mesopores. Solid-state nuclear magnetic resonance revealed that long hydrocarbon macromolecules readily move within the pores of this catalyst, with a subsequent escape being inhibited by polymer–surface interactions, a behaviour that resembles the binding and translocation of macromolecules in the catalytic cleft of processive enzymes. Accordingly, the hydrogenolysis of polyethylene with this catalyst proceeds processively to yield a reliable, narrow and tunable stream of alkane products.

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

Creating values from wastes: Producing biofuels from waste cooking oil via a tandem vapor-phase hydrotreating process

Here, this study is focused on producing biofuels from waste oils via a tandem vapor-phase hydrotreating process in a pressurized two-stage fixed bed reactor over a bifunctional Ni/Al 2 O 3 -SiO 2 catalyst under 0.25 MPa H 2 . A 100% hydrodeoxygenation efficiency both in liquid and gas products was observed, yielding 83.9 wt% C 5 -C 19 n-alkanes which corresponds to a 7.4-fold increase compared with that obtained from non-catalytic conversion. The hydrodeoxygenation mechanism of waste cooking oil in the catalytic tandem hydrotreating process induced by Ni/Al 2 O 3 -SiO 2 was proposed. The hydropyrolysis temperature in the first reactor, hydrogenation temperature in the second reactor, reaction pressure, catalyst to waste cooking oil mass ratio, and gas hourly space velocity (GHSV) was optimized at 550 °C, 300 °C, 0.25 MPa, 3, and 56 s -1 , respectively. The application potential of this cascade vapor-phase hydrotreating process was evaluated by employing different waste oils such as palm kernel oil, woody oil (swida wilsoniana), soapstock, and waste lubricating oil as feedstock, giving C 5 to C 19 n-alkane yields ranging from 21.6 to 87.5 wt%. This work provides a novel and promising approach to upcycle waste oils into upgraded biofuels compared with conventional catalytic pyrolysis.

09 BIOMASS FUELS↗
DOE OSTI2021

CO 2 electro-reduction on Cu 3 P: Role of Cu(I) oxidation state and surface facet structure in C 1 -formate production and H 2 selectivity

We report the catalytic activity and mechanism of copper(I) phosphide, Cu 3 P, with predominant [00Ι] facet exposure for the electrochemical reduction of CO 2 (CO 2 RR) to formic acid. Crystalline nanosheets of this compound that show a preferential [00Ι] facet orientation exhibit undiminished CO 2 RR activity after 16 hours with full retention of crystal structure and surface chemical speciation and no detectable corrosion. In contrast to the range of products formed on Cu metal, CuO, and Cu 2 O, the CO 2 RR on Cu 3 P [00Ι] produces mainly hydrogen and formate as the sole carbon product in KHCO 3 electrolyte. Analysis of the Cu 3 P [00Ι] facet by HAADF-STEM was used to determine the surface lattice structure, while both XPS and Auger spectroscopies were used to determine the surface chemical speciation from the kinetic energies of ionized electrons. The presented analysis identifies isolated trigonal CuP 3 sites on the Cu 3 P[00Ι]-Cu 3 P 3 terminated surface and the Cu(I) oxidation state as precursor to the active catalyst. The CO 2 RR selectivity to formate and the higher turnover rate for H 2 production on the [00Ι] facet allows a structure-activity analysis and chemical mechanism to be proposed. Formation of a surface hydride at isolated *H-CuP 3 sites is proposed as the catalytic site in forming both H 2 and formate, while the long Cu—Cu separation retards forming C-C coupling products. In conclusion, these results disprove previously published claims of Cu(I) oxidation state as a sufficient criterion to promote CO 2 RR to C 2+ products, show that stronger bonded hydrides, *H-CuP 3 on Cu 3 P, favor production of the C1 product formate over all other carbon products, and predict that stronger formate binding (bidentate) is needed for CO 2 RR currents to compete with H 2 production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2018

Development of a Detailed Surface Chemistry Framework in DSMC

A generalized finite-rate surface chemistry framework incorporating a comprehensive list of reaction mechanisms is developed and implemented into the Direct Simulation Monte Carlo (DSMC) solver SPARTA (Stochastic PArallel Rarefied-gas Time-accurate Analyzer). The various mechanisms include adsorption, desorption, Eley-Rideal (ER), and several types of Langmuir-Hinshelwood (LH) mechanisms. The approach is to stochastically model the various competing reactions occurring on a set of active sites. Both gas-surface (e.g., adsorption, ER) and pure-surface (e.g., desorption) reaction mechanisms are incorporated, and the framework also includes catalytic or surface altering mechanisms involving the participation of the bulk-phase species (e.g., bulk carbon atoms). Marschall and MacLean developed a general formulation in which multiple phases and surface sites are used and a similar convention is adopted in the current work. Expressions for the microscopic parameters of reaction probabilities (for gas-surface reactions) and frequencies (for pure-surface reactions) that are required for DSMC are derived from the surface properties and macroscopic parameters such as rate constants, sticking coefficients, etc. The energy and angular distributions of the products are specified according to the reaction type and input parameters. This framework also presents physically consistent procedures to accurately compute the reaction probabilities and frequencies in the case of multiple reactions. The result is a modeling tool with a wide variety of surface reactions characterized via user-specified reaction rate constants, surface properties and parameters.

Surface Chemistry↗
DOE OSTI2021

Catalytic materials for lithium-sulfur batteries: mechanisms, design strategies and future perspective

Lithium-sulfur batteries (LSBs) are attractive candidates for post-lithium-ion battery technologies because of their ultrahigh theoretical energy density and low cost of active cathode materials. However, the commercialization of LSBs remains extremely challenging primarily due to poor cycling performance and safety concerns, which are inherently caused by low conductivity of S 8 and Li 2 S, severe polysulfide shuttling, and high polarization by solid Li 2 S 2 /Li 2 S deposition. Catalytic materials could facilitate the large-scale practical application of LSBs by overcoming all these challenges. In this review, we investigate the sulfur species evolution in LSBs and explore the roles of catalytic materials in charge/discharge processes, highlighting the catalysis of solid S 8 to liquid polysulfides and solid Li 2 S 2 to Li 2 S. Furthermore, we offer systematic strategies from atomic to macro levels, including defect engineering, morphology engineering and catalyst compositing, to enhance catalysis efficiency in terms of sulfur supercooling, fast charge transfer, thiosulfate generation, disulfide bond cleavage, tuneable Li 2 S growth and Li 2 S decomposition enhancement. Finally, the design and availability of the proposed catalytic materials will further advance LSB technology from coin cells and pouch cells to the subsequent commercialization scale.

25 ENERGY STORAGE↗
DOE OSTI2021

Kinetic Measurements in Heterogeneous Catalysis

This contribution is about the experimental determination of the rate of a heterogeneous catalytic reaction and the analysis of kinetic data. In this case, the reaction rate can be defined as the frequency at which the closed sequence of elementary steps transforming reactants into products is occurring. However, the rate of chemical reaction is not directly observed; rather, one records the rate of substance change. The rate of chemical reaction is calculated based on the rate of substance change and assumed stoichiometry of the reaction. In order to make this an intensive quantity (i.e., independent of the volume in which the reaction is performed, this frequency is divided by the latter or by a quantity proportional to the latter). As the focus of what follows is on heterogeneously catalyzed reactions this can be the catalyst mass, the catalyst surface area or the total number of active sites present in the reaction volume confined by the walls of a chemical reactor. For example, the rate may be reported as one of the following: Net rate of consumption/production of component i mol m-3 s-1 Net specific rate of consumption/production of component i mol kg-1 s-1 Rate of substance change (per unit volume of catalyst) mol m-3 s-1 Specific reaction rate (per unit mass of catalyst) mol kg-1 s-1 Net rate of consumption/production of component i mol m-2 s-1 The turnover frequency (TOF) is a characteristic originally introduced by Boudart [1] is expressed as TOF=R/G_tot , where R is the steady-state rate of reactant consumption or product generation and G_totis the total areal density of active sites [mol m-2]. The latter is typically taken from experimental chemisorption data obtained at low temperature. The advancement of a chemical reaction leads to changes in the amounts of reactants and products which, for a stoichiometric single reaction, are connected by the stoichiometric coefficients. In many cases, for the sake of simplicity, we will assume that the investigated reaction proceeds according to a single reaction pathway, so that the net production rate of a reaction component is directly proportional to the reaction rate and that the latter equals the net production rate of any of the involved components when divided by the appropriate stoichiometric coefficient. For complex stoichiometric reactions the net production rates of the involved components are linear combinations of the reaction rates. Different goals for kinetic measurements can be formulated: Catalyst testing, i.e., obtaining the kinetic dependences for the development and discrimination of efficient catalytic materials. Precise kinetic characterization of active materials via high-throughput screening is a part of such activity. Detailed kinetics, i.e., revealing the detailed mechanism of complex catalytic reaction via systematic kinetic studies, both steady-state and non-steady-state Industrial kinetics, i.e., obtaining data and relationships for describing and predicting the behaviour of catalytic reactors and processes at industrial scale Finally, mathematical modeling and analysis where kinetic measurements provide data for understanding complex kinetic phenomena, e.g., oscillations, non-linear self-organization, etc.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Modeling of carbon monoxide oxidation kinetics over NASA carbon dioxide laser catalysts

The recombination of CO and O2 formed by the dissociation of CO2 in a sealed CO2 laser discharge zone is examined. Conventional base-metal-oxide catalysts and conventional noble-metal catalysts are not effective in recombining the low O2/CO ratio at the low temperatures used by the lasers. The use of Pt/SnO2 as the noble-metal reducible-oxide (NMRO), or other related materials from Group VIIIA and IB and SnO2 interact synergistically to produce a catalytic activity that is substantially higher than either componet separately. The Pt/SnO2 and Pd/SnO2 were reported to have significant reaction rates at temperatures as low as -27 C, conditions under which conventional catalysts are inactive. The gas temperature range of lasers is 0 + or - 40 C. There are three general ways in which the NMRO composite materials can interact synergistically: one component altering the properties of another component; the two components each providing independent catalytic functions in a complex reaction mechanism; and the formation of catalytic sites through the combination of two components at the atomic level. All three of these interactions may be important in low temperature CO oxidation over NMRO catalysts. The effect of the noble metal on the oxide is discussed first, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Herz, Richard K.↗