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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Understanding the origin of structure sensitivity in hydrodechlorination of trichloroethylene on a palladium catalyst

Periodic density functional theory (DFT) calculations are employed to understand the origin of structure sensitivity in hydrodechlorination (HDC) of trichloroethylene (TCE) over different facets of a palladium catalyst. The HDC reaction is simulated on the terrace (Pd (111) and Pd (100)) and undercoordinated (Pd (211) and Pd (110)) sites of the Pd catalyst. The most stable binding configuration of TCE on the Pd surfaces is observed to be through the di-σ mode of binding, wherein each carbon atom of the TCE molecule is adsorbed atop of the Pd atom. On comparing TCE adsorption over different facets of Pd, a maximum binding energy of –178 kJ mol –1 is calculated over the Pd (110) surface. TCE, upon adsorption on Pd catalyst, undergoes dechlorination followed by hydrogenation of the hydrocarbon intermediates. The activation energies for C–Cl bond dissociation steps are significantly low when compared to the hydrogenation steps. The chlorine released from dechlorination tends to block the active sites, thereby poisoning the surface with high binding energies (B.E > –160 kJ mol –1 ) on all the surfaces. The trend in chlorine binding energies on Pd facets follows: Pd (110) > Pd (211) > Pd (100) > Pd (111). The removal of surface chlorine is facilitated by its reaction with surface hydrogen to form hydrogen chloride. The activation energy for hydrogen chloride formation is calculated to be 90 kJ mol –1 and 88 kJ mol –1 on Pd (111) and Pd (100) terrace sites, respectively and 109 kJ mol –1 and 118 kJ mol –1 on the step Pd (211) and corrugated Pd (110) facets, respectively. This suggests the ease of removal of Cl as HCl from the terrace sites as compared to the step and corrugated sites. The structure sensitivity in the TCE HDC reaction could possibly arise due to the differences in the energetics of Cl removal on different Pd facets. As a result, this mechanistic understanding could provide a rationale for designing suitable catalysts for the HDC of TCE.

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

Binding of Sulfates and Water to Monovalent Cations

The binding of the sulfate ligand group to monovalent cations in the presence of water is important for many systems. To understand the structure and energetics of sulfate complexes, we use density functional theory to study ethyl sulfate binding to the monovalent cations Li + , Na + , and K + , and to water. The free energies of binding and optimal structures are calculated for a range of the number of ethyl sulfates and waters. Without water, the most optimal structure for all the cations is bidentate binding by two ethyl sulfates, yielding a 4-fold coordination. With water, the lowest free energy structures also have two ethyl sulfates, but the coordination varies with cations. For complexes with water, the four oxygen atoms in the sulfate group enable multiple binding geometries for the cations and for hydrogen bonding with water. Many of these geometries differ in free energy by only a small amount (1–2 kcal/mol), meaning there will be multiple binding configurations in bulk solution. In comparison to the optimal structures for binding to the carboxylate group, there is more variation for binding to the sulfate group as a function of cation type and the number of waters. Further, the polarization of the atoms is significant and varies among the sulfate oxygen atoms. The water oxygen charge is often larger than that of sulfate oxygen, which plays a role in the preference for monodentate ligand binding to cations in the presence of water.

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

Investigations of Relative Stability and Distribution of Mo Species in Pore Space of Mo/ZSM-5 Systems

Reduced forms of molybdenum (Mo) carbides anchoring in pore space of zeolites are considered as activated catalysts for the methane dehydroaromatization reaction. However, the atomic structure of the active sites and their stability under reactive conditions are still not clearly understood. Herein, we employ a synergistic theoretical and experimental approach to investigate this research gap. The Raman data shows the existence of the distributed binuclear and mononuclear Mo oxides in the pores that are corroborated by the hydrogen temperature-programmed reduction experiments. The binding free energies of mono- and bi-nuclear Mo carbides in straight and sinusoidal channels and their intersections as a function of temperature and anchoring sites have been determined. The catalysts with Mo coordinated at two anchoring sites are more stable compared to those located at the rings with one Al substitution. The activation energies of the catalysts migration to adjacent rings were estimated as a function of temperature and kinetics parameters of such migrations were determined. The migration is facilitated if there is one anchoring site shared between two rings. This process can contribute to an agglomeration mechanism leading to loss of catalytic activity.

Myshakin, Evgeniy↗
DOE OSTI2021

High Ammonia Adsorption in MFM-300 Materials: Dynamics and Charge Transfer in Host–Guest Binding

Ammonia (NH 3 ) is a promising energy resource owing to its high hydrogen density. However, its widespread application is restricted by the lack of efficient and corrosion-resistant storage materials. In this work, we report high NH 3 adsorption in a series of robust metal-organic framework (MOF) materials, MFM-300(M) (M = Fe, V, Cr, In). MFM-300(M) (M = Fe, V III , Cr) show fully reversible capacity for >20 cycles, reaching capacities of 16.1, 15.6, and 14.0 mmol g -1 , respectively, at 273 K and 1 bar. Under the same conditions, MFM-300(V IV ) exhibits the highest uptake among this series of MOFs of 17.3 mmol g -1 . In situ neutron powder diffraction, single-crystal X-ray diffraction, and electron paramagnetic resonance spectroscopy confirm that the redox-active V center enables host-guest charge transfer, with V IV being reduced to V III and NH 3 being oxidized to hydrazine (N 2 H 4 ). A combination of in situ inelastic neutron scattering and DFT modeling has revealed the binding dynamics of adsorbed NH 3 within these MOFs to afford a comprehensive insight into the application of MOF materials to the adsorption and conversion of NH 3 .

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

Intermolecular Interactions in Direct Air Capture Materials: Insights from Charge Density Analysis

Direct air capture (DAC) materials enable the removal of CO 2 from the atmosphere, but improving their efficiency requires a detailed understanding of the intermolecular interactions that govern CO 2 sorption and release. Here, we present an experimental electron density study of methylglyoxal-bis(iminoguanidine) (MGBIG), a promising DAC material, using high-resolution X-ray and neutron diffraction data combined with quantum crystallographic analysis. This approach bridges theoretical and experimental data by quantifying electron density distributions and revealing how hydrogen bonds stabilize CO 2 -derived carbonate phases and may influence the desorption behavior. We identify distinct hydrogen-bonding environments in two crystalline carbonate phases: P1, a transient kinetic product, and P3, a thermodynamically stable phase. Multipolar refinement and electrostatic potential and multipole moment calculations precisely map electron density distributions, revealing key hydrogen bonds involved in CO 2 capture. Topological analysis of electron density highlights a cooperative hydrogen-bonding network in the thermodynamically favored P3 phase, where enhanced electron density delocalization and water-mediated interactions contribute to a more stable lattice. Energetic analyses confirm that stronger hydrogen bonding networks enhance the stability of P3 with a binding energy of −607.0 kJ/mol and greater lattice stability (−847.3 kJ/mol) compared to P1 (−302.5 and −571.0 kJ/mol, respectively). Electrostatic potential maps further illustrate polarization patterns that may influence the stability of the binding of CO 2 and release conditions. These findings establish a direct experimental framework for linking electron density distributions to intermolecular interactions in DAC materials, providing a rational design strategy for optimizing sorbents with improved CO 2 capture efficiency and reduced energy demands.

Electron density↗
DOE OSTI2025

Catalytic Activity of an Ensemble of Sites for CO 2 Hydrogenation to Methanol on a ZrO 2 -on-Cu Inverse Catalyst

The significant increase in CO 2 emissions from heavy fossil fuel utilization has raised serious concerns, highlighting the need for effective methods to convert CO 2 into value-added chemicals. Here, in this work, we report a computational investigation on the catalytic activity of ZrO 2 -on-Cu inverse catalysts for CO 2 hydrogenation to methanol, considering highly dispersed ZrO 2 trimers on Cu (111). Such clusters present a large ensemble of formate-containing configurations, Zr 3 O n (OH) m (OCHO) l , making the evaluation of the catalytic activity very challenging. We found that the sites on the various catalyst configurations exhibit markedly different activities for formate hydrogenation, despite their similar free energy and composition. To understand these differences in reactivity, we examined the structural and electronic nature of the low free-energy catalyst configurations and identified that the energy of the lowest unoccupied orbital of the reacting formate, modified by its binding with the catalytic site, is a descriptor for the reaction energy of the formate hydrogenation step. From there, we screened an ensemble of catalyst structures using this descriptor to predict highly active metastable catalyst configurations and computed the reaction pathways and transition states for formate hydrogenation. From this investigation, we distinguished reactive from nonreactive sites and formate species on the ZrO 2 /Cu inverse catalyst based on structural and electronic features. We showed that rare metastable configurations control the activity. Additionally, an efficient method for examining the reactivity of a large number of coexisting catalyst structures was developed.

catalysts↗
DOE OSTI2025

Subsurface hydrogen, curvature, and strain: lessons from electro-reduction of benzaldehyde on nano-structured Pd catalysts

The unique ability of palladium (Pd) to absorb hydrogen and form a bulk hydride is vital for chemical transformations that involve hydrogenation reactions. Nano-structured Pd catalysts offer a promise of tuning these reaction rates by exploiting variations of reactant binding energies depending on the surface structure and morphological constraints that result in inhomogeneous strain. However, the interplay between the nano-structure of Pd and the ability of Pd to adsorb (and absorb) hydrogen as well as other reactive species needs to be better understood for a rational understanding of competitive chemical transformations at Pd surfaces. We consider the effects of the surface corrugation, strain, and subsurface Pd hydride on the reduction of benzaldehyde to benzyl alcohol in two qualitatively different samples – Pd nanoparticles and Pd gels formed by quasi-one-dimensional chains of these nanoparticles. Our electrochemical measurements and computational modelling suggest that surface concave sites, inherent to Pd gels, facilitate hydrogen transfer to the Pd subsurface region, thus weakening benzaldehyde binding to the surface. This effect is further modulated by the strain, depending on the local coordination environment on the corrugated surface. Furthermore, these findings demonstrate how structurally complex samples in the form of gels provide degrees of freedom for controlling the behavior of metal catalysts that are not available in isolated nanoparticles, which paves the way for new approaches in the design of catalytic materials and synthesis of metal hydrides.

Padavala, Sri Krishna Murthy [University of Minnes↗
DOE OSTI2020

In silico discovery of active, stable, CO-tolerant and cost-effective electrocatalysts for hydrogen evolution and oxidation

Various databases of density functional theory (DFT) calculations for materials and adsorption properties are currently available. Using the Materials Project and GASpy databases of material stability and binding energies (H* and CO*), respectively, we evaluate multiple aspects of catalysts to discover active, stable, CO-tolerant, and cost-effective hydrogen evolution and oxidation catalysts. Finally, we suggest a few candidate materials for future experimental validations. We highlight that the stability analysis is easily obtainable but provides invaluable information to assess thermodynamic and electrochemical stability, bridging the gap between simulations and experiments. Furthermore, it reduces the number of expensive DFT calculations required to predict catalytic activities of surfaces by filtering out unstable materials.

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

Fluorinated Covalent Organic Frameworks: A Novel Pathway to Enhance Hydrogen Sorption and Control Isosteric Heats of Adsorption; HyMARC Seed Project Final Report

Organic framework materials, as a unique sub-class of carbon-based sorbents, have gained increasing attention for promising attributes toward gas storage. Calculations of the hydrogen capacity of optimized frameworks show potential to achieve greater than 60 g/L storage of hydrogen, placing metal-organic frameworks (MOFs) and COFs near the top of the class of porous materials. However, at the ensemble level, poor stacking creates a quasi-amorphous material with low structural integrity and low effective surface area. The chemical versatility of COFs allows for additional methods for producing long-range order that specifically target the inter-layer interactions in COFs but that leave key pore-accessible linker sites open. These modifications (either during synthesis or post-synthetic) enable a host of strategies to both improve crystalline order for more stable and higher surface, as well as add metals with open coordination for enhanced H 2 binding enthalpy.

08 HYDROGEN↗
DOE OSTI2026

Electronegativity-Guided Site Differentiation in High-Entropy Alloy for pH-universal Hydrogen Evolution Reactions

Enhancing the intrinsic activity of transition metal catalysts for the hydrogen evolution reaction (HER) remains a critical challenge in sustainable energy conversion. Herein, we report an electronegativity-guided site differentiation strategy in a single-phase CoNiCuMoW high-entropy alloy (HEA) via electrodeposition by incorporating high-electronegativity 4d/5d orbital transition metals (Mo, W) into the face-centered cubic (fcc) matrix (CoNiCu). The as-synthesized HEA demonstrates exceptional HER performance in all pH conditions, delivering an outstanding overpotential of 65 mV (alkaline), 28 mV (acidic), and 155 mV (neutral) at a current density of 100 mA cm−2, showing performance comparable to commercial Pt/C and has excellent long-term stability at high current density (1 A cm−2, 1000 h). X-Ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations reveal that the incorporation of Mo/W simultaneously alters the local coordination environment and induces element-dependent charge redistribution, accompanied by a system-level d-band center downshift, thereby optimizing the hydrogen binding strength across multimetallic sites. Meanwhile, oxophilic Mo/W sites lower the water dissociation energy barrier. These synergistic effects collectively enable efficient and durable pH-universal HER performance.

Wu, Yutong↗
DOE OSTI2020

Density Functionals for Hydrogen Storage: Defining the H2Bind275 Test Set with Ab Initio Benchmarks and Assessment of 55 Functionals

Efficient and high-capacity storage materials are indispensable for a hydrogen-based economy. In silico tools can accelerate the process of discovery of new adsorbent materials with optimal hydrogen adsorption enthalpies. Density functional theory is well-poised to become a very useful tool for enabling high-throughput screening of potential materials. In this work, we have identified density functional approximations that provide good performance for hydrogen binding applications following a two-pronged approach. First, we have compiled a data set (H2Bind275) that comprehensively represents the hydrogen binding problem capturing the chemical and mechanistic diversity in the binding sites encountered in hydrogen storage materials. We have also computed reference interaction energies for this data set using coupled-cluster theory. Second, we have assessed the performance of 55 density functional approximations for predicting H 2 interaction energies and have identified two hybrid density functionals (ωB97X-V and ωB97M-V), two double hybrid density functionals (DSD-PBEPBE-D3(BJ) and PBE0-DH), and one semilocal density functional (B97M-V) as the best performing ones. We have recommended the addition of empirical dispersion corrections to systematically underbinding density functionals such as revPBE, BLYP, and B3LYP for improvements in performance at negligible additional cost. We have also recommended the usage of the def2-TZVPP basis set as it represents a good compromise between accuracy and cost, limiting the finite basis set errors to less than 1 kJ/mol.

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

Influence of Heat Treatments in H 2 and Ar on the E 1 center in β -Gs 2 O 3

In this report the influence of heat treating n-type bulk β-Ga 2 O 3 in hydrogen (H2) and argon (Ar) gases on the presence of the defect level commonly labeled as E 1 was studied. Fourier transform-infrared spectroscopy confirms that hydrogen (H) is incorporated into β-Ga 2 O 3 during H 2 annealing at 900 °C. Deep-level transient spectroscopy measurements reveal that the concentration of the E 1 level is promoted by the introduction of H, in contrast to what is observed in samples heat-treated in an Ar flow. We further find the E 1 level to be stable against heat treatments at 650 K, both with and without an applied reverse-bias voltage. Potential candidates for the defect origin of E 1 are investigated using hybrid-functional calculations, and three types of defect complexes involving H are found to exhibit charge-state transition levels compatible with E 1 , including substitutional H at one of the threefold coordinated O sites, Ga-substitutional shallow donor impurities passivated by H, and certain configurations of singly hydrogenated Ga–O divacancies. Among these types, only the latter exhibit H binding energies that are consistent with the observed thermal stability of E 1 .

36 MATERIALS SCIENCE↗
DOE OSTI2023

An extensive assessment of the performance of pairwise and many-body interaction potentials in reproducing ab initio benchmark binding energies for water clusters n = 2–25

We assess the performance of 7 pairwise additive (TIP3P, TIP4P, TIP4P-ice, TIP5P, OPC, SPC, SPC/E) and 8 families of many-body potentials (q-AQUA, HIPPO, AMOEBA, EFP, TTM, WHBB, MB-pol, MB-UCB) in reproducing high-level ab initio benchmark values, CCSD(T) or MP2 at the complete basis set (CBS) limit for the binding energy and the many-body expansion (MBE) of water clusters n = 2–11, 16–17, 20, 25. By including a large range of cluster sizes having dissimilar hydrogen bonding networks, we obtain an understanding of how these potentials perform for different hydrogen bonding arrangements that are mostly outside of their parameterization range. While it is appropriate to compare the results of ab initio based many-body potentials directly to the electronic binding energies (D e 's), the pairwise additive ones are compared to the enthalpies at T = 298 K, ΔH(298 K), as the latter class of force fields are parametrized to reproduce enthalpies (implicitly accounting for zero-point energy corrections) rather than binding energies. We find that all pairwise additive potentials considered overestimate the reference ΔH values for the n = 2–25 clusters by >13%. For the water dimer (n = 2) in particular, the errors are in the range 83–119% for the pairwise additive potentials studied since these are based on an effective rather than the true 2-body interaction specifically designed as a means of partially accounting for the missing many-body terms. This stronger 2-body interaction is achieved by an enhanced monomer dipole moment that mimics its increase from the gas phase monomer to the condensed phase value. Indeed, for cluster sizes n ≥ 4 the percent deviations become slightly smaller (albeit all exceeding 13%). In contrast, we find that the many-body potentials perform more accurately in reproducing the electronic binding energies (D e 's) throughout the entire cluster range (n = 2–25), all reproducing the ab initio benchmark binding energies within ±7% of the respective CBS values. We further assess the ability of a subset of the many-body potentials (MB-UCB, q-AQUA, MB-pol, and TTM2.1-F) to also reproduce the magnitude of the ab initio many-body energy terms for water cluster sizes n = 7, 10, 16 and 17. The potentials show an overall good agreement with the available benchmark values. However, we identify characteristic differences upon comparing the many-body terms at both the ab initio-optimized geometries and the respective potential-optimized geometries to the reference ab initio values. Additionally, by applying this analysis to a wide range of cluster sizes, trends in the MBE of the potentials with increasing cluster size can be identified. Finally, in an attempt to draw a parallel between the pairwise additive and many-body potentials, we report the analysis of the individual molecular dipole moments for water clusters with 1 to ~4 solvation shells with the TTM2.1-F potential. We find that the internally solvated water molecules have in general a larger molecular dipole moment ranging from 2.6–3.0 D. This justifies the use of an enhanced, with respect to the gas-phase value, molecular dipole moment for the pairwise additive potentials, which is intended to fold in the many body terms into an effective (enhanced) pairwise interaction through the choice of the charges. These results have important implications for the development of future generations of efficient, transferable, and highly accurate classical interaction potentials in both the pairwise additive and many-body categories.

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

Electrochemical CO 2 Reduction Reaction over Cu Nanoparticles with Tunable Activity and Selectivity Mediated by Functional Groups in Polymeric Binder

Electrochemical carbon dioxide reduction reaction (CO 2 RR) using copper (Cu)-based catalysts has received significant attention mainly because Cu is an element capable of producing hydrocarbons and oxygenates. One possible way to control the CO 2 RR performance at the electrode interface is by modifying catalysts with specific functional groups of different polymeric binders, which are necessary components in the process of electrode fabrication. However, the modification effect of the key functional groups on the CO 2 RR activity and selectivity is poorly understood over Cu-based catalysts. In this work, the role of functional groups (e.g., -COOH and -CF 2 groups) in hydrophilic and hydrophobic polymeric binders on the CO 2 RR of Cu-based catalysts is investigated using a combination of electrochemical measurements, in-situ characterization and density functional theory (DFT) calculations. DFT results reveal that functional groups influence the binding energies of key intermediates involved in both CO 2 RR and the competing hydrogen evolution reaction, consistent with experimental observation of binder-dependent product distributions among formic acid, CO, CH 4 , and H 2 . This study provides a fundamental understanding that the selection of desired polymeric binders is a useful strategy for tuning the CO 2 RR activity and selectivity.

25 ENERGY STORAGE↗
DOE OSTI2021

Hydrogenation and C-S bond activation pathways in thiophene and tetrahydrothiophene reactions on sulfur-passivated surfaces of Ru, Pt, and Re nanoparticles

Thiophene-H2 reactions proceed via sulfur removal and hydrogenation routes on dispersed metal nanoparticles that become decorated by refractory S-adlayers during catalysis. The identity and kinetic relevance of the required elementary steps are described here based on rates measured at S-chemical potentials set by H2S/H2 ratios similar to those prevalent during practical catalysis on Re, ReSx, Ru, and Pt catalysts. Free energies for S adatom formation (from H2S decomposition and H2 evolution) are strongly exothermic (< -50 kJ mol-1 on Pt(111) and < -150 kJ mol-1 on Re and Ru(0001)), but strong repulsions between S adatoms cause adsorption free energies to increase significantly with coverage on all three surfaces, preventing complete monolayer formation. These adlayers, composed of unreactive S-atoms (S') that cover 1/3–2/3 ML leave residual interstitial spaces (*) that bind S-atoms (S*), intermediates, and transition states reversibly, as required for catalytic turnovers. The number and binding properties of these interstices depend on the identity and chemical state of the nanoparticle bulk phase, which influences S'-binding and coverages and cause large differences in direct desulfurization and hydrogenation turnover rates (per exposed metal atom) on dispersed Re, ReSx, Ru, and Pt. The identity and kinetic relevance of elementary steps for desulfurization (to C4¬ hydrocarbons) and hydrogenation (to tetrahydrothiophene; THT) are similar among these catalysts; they involve the kinetically-relevant formation of a thiophene-derived intermediate (monohydrothiophene on Re and ReSx; dihydrothiophene on Ru and Pt) that either cleaves its C-S bond or “over-hydrogenates” to THT in one surface sojourn. THT then undergoes C-S bond cleavage in secondary reactions that correct such over-hydrogenation to form the more unsaturated species that cleave C-S bonds. THT/C4 product ratios are insensitive to H2S/H2 ratios and thiophene pressure, even though active interstitial spaces are covered by kinetically-detectable coverages of S* and thiophene; therefore, primary and secondary reactions must involve the same active surfaces. The observed increase in THT/C4 ratios with H2 pressure shows that THT formation transition states involve a larger number of H-atoms than for C-S cleavage. The requirement for bound species with intermediate unsaturation (between THT and thiophene) for C-S bond cleavage is reminiscent of the H-shuttling required in C-C and C-O hydrogenolysis, reactions that involve the partial dehydrogenation of alkanes and alkanols, respectively, to weaken such bonds and to increase the formation entropy of the relevant transition states via the evolution of H2(g). These mechanistic details challenge prevalent paradigms about different site requirements for hydrogenation and desulfurization pathways and about how metal-sulfur bond energies act as descriptors of reactivity; in fact, such binding energies merely act to define the refractory S-adlayers that enable the formation of weakly-binding interstices that reversibly bind intermediates and transition states, thus allowing catalytic turnovers.

Yik, Edwin↗
DOE OSTI2019

Structure and regulation of human epithelial cell transforming 2 protein

Epithelial cell transforming 2 (Ect2) protein activates Rho GTPases and controls cytokinesis and many other cellular processes. Dysregulation of Ect2 is associated with various cancers. Here, we report the crystal structure of human Ect2 and complementary mechanistic analyses. The data show the C-terminal PH domain of Ect2 folds back and blocks the canonical RhoA-binding site at the catalytic center of the DH domain, providing a mechanism of Ect2 autoinhibition. Ect2 is activated by binding of GTP-bound RhoA to the PH domain, which suggests an allosteric mechanism of Ect2 activation and a positive-feedback loop reinforcing RhoA signaling. Furthermore this bimodal RhoA binding of Ect2 is unusual and was confirmed with Förster resonance energy transfer (FRET) and hydrogen–deuterium exchange mass spectrometry (HDX-MS) analyses. Several recurrent cancer-associated mutations map to the catalytic and regulatory interfaces, and dysregulate Ect2 in vitro and in vivo. Together, our findings provide mechanistic insights into Ect2 regulation in normal cells and under disease conditions.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Catalytic influence of light element incorporation in the lattice of palladium

The alloying of metals with foreign elements is a common approach for manipulating catalytic properties of active sites. For palladium-based catalysts, incorporation of light elements receives far less attention than Pd-metal alloys even though incorporated light element are catalytically significant. Due to their small size, light elements (H, B, C, and O) can occupy octahedral sites in Pd to form an interstitial phase, while palladium adjusts its lattice to accommodate the incorporation of larger light elements (S and P) to form distinct phases. The incorporated light element modifies the electronic structure of palladium, influencing the binding energy of substrates and reactive intermediates. Pd hydride and oxide often form in situ during hydrogenation or oxidation reactions, respectively, representing the (more, less) active phase of the catalyst. Further, the reactive interstitial hydrogen dissolved in Pd tends to hydrogenate reactants completely and unselectively. Pd oxide can be the active phase for oxidation reactions, and the incorporated oxygen or oxygen vacancies may participate in the reaction directly. Incorporated light elements change geometric aspects of Pd ensembles, serving the role of site blocking, ensemble isolation, or serve as an additional active site, endowing Pd with bifunctional character. We review the synthetic approaches for incorporating light elements into the palladium lattice. We summarize the catalytic influence of light element incorporation into the palladium lattice with respect to electronic and geometric modification, in situ incorporated hydrogen and oxygen, and discuss the influence of light element incorporation into Pd on specific reactions (i.e., selective hydrogenation, oxidation, electrocatalysis, and C—C cross coupling).

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

Development of Density Functional Tight-Binding Parameters Using Relative Energy Fitting and Particle Swarm Optimization

We provide a strategy to optimize density functional tight-binding (DFTB) parameterization for the calculation of the structures and properties of organic molecules consisting of hydrogen, carbon, nitrogen, and oxygen. We utilize an objective function based on similarity measurements and the Particle Swarm Optimization (PSO) method to find an optimal set of parameters. This objective function considers not only the common DFTB descriptors of binding energies and atomic forces but also incorporates relative energies of isomers into the fitting procedure for more chemistry-driven results. The quality in the description of the binding energies and atomic forces is measured based on the Ballester similarity index and relative energies through a similarity index induced by the Levenshtein edit distance to quantify the correct energetic order of isomers. Training and testing datasets were created to include all relevant chemical functional groups. Finally, the accuracy of this strategy is assessed, and its range of applicability is discussed by comparison against our previous parameterization. The improved performance of the new DFTB parameterization is validated with respect to the density functional theory large datasets QM-9 and ANI-1, where excellent agreement is found between the structures and properties available in these datasets, and the ones obtained with DFTB.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗