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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Fundamental Interactions of Bimetallic Cu x Pd y ( x + y = 4) Clusters Supported on the α-WC(0001) Surface and Their Performance for CO 2 Adsorption and Dissociation

The tungsten carbide α-WC(0001) surface, an active system for the activation of H 2 and important hydrogenation processes involving unsaturated hydrocarbons, can serve as a support of bimetallic clusters to produce materials with unique catalytic properties, opening routes for a wide range of technical applications. In particular, Cu x Pd y clusters are of particular interest because they combine metals with different properties. A stochastic method was applied to obtain the geometry of Cu x Pd y (x + y = 4) bare clusters, evaluating thousands of possibilities to obtain stable structures, yielding one isomer for Cu 4 , Cu 2 Pd 2 , Cu 1 Pd 3 , and Pd 4 and two isomers for Cu 3 Pd 1 . These clusters were supported on C and W terminations of the tungsten carbide (0001) surface, exploring all of the binding possibilities. The adsorption energies on the C and W terminations are in the ranges from −2.51 to −3.02 eV and from −2.26 to −3.30 eV, respectively. The strongest and weakest binding was seen for monometallic Cu 4 and Pd 4 clusters on both C and W terminations, while the Cu-Pd bimetallics have intermediate adsorption energies but lack a clear trend in terms of composition. The location of Cu x Pd y clusters over the (0001) surface induces a decrease in the work function relative to the pristine surface, while the cluster-surface Bader charge transfer and variations in the partial density of states point to changes in the electronic structure of the carbide atoms upon binding of the metallic clusters. The d-band center of the Cu x Pd y deposited on WC(0001) indicates an intermediate reactivity among Cu(111) and Pd(111) surfaces, modulating the reactivity with small numbers of Cu and Pd atoms, i.e., atom economy in catalyst design. The likelihood of existence of the most stable Cu x Pd y (x + y = 4) clusters in the temperature range of 298-400 K is 100%. The composite Cu x Pd y /α-WC(0001) (x + y = 4), is a nontrivial system since 22 isomers are needed to completely describe its structural properties. Among the isomers, seven structures are necessary to represent Cu 3 Pd 1 /α-WC(0001), five for Pd 4 /α-WC(0001), two for Cu 4 /α-WC(0001), and four for Cu 2 Pd 2 /α-WC(0001) and Cu 1 Pd 3 /α-WC(0001). The large number of cluster isomers supported on the tungsten carbide surface opens the door for several applications in the heterogeneous catalysis of the Cu x Pd y /α-WC(0001) composite, with the possibility of modulating the geometric, electronic, and chemical properties according to a desired application. Test studies for the adsorption of CO 2 indicate that the Cu x Pd y /α-WC(0001) composites are highly active for the adsorption and decomposition of the molecule, with bimetallic and admetal-carbide interactions playing a key role in the binding performance. In conclusion, this high activity indicates that these systems should be useful as catalysts for the conversion of CO 2 to oxygenates or light alkanes.

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

Boosting CO 2 Electrochemical Reduction with Atomically Precise Surface Modification on Gold Nanoclusters

Thiolate-protected gold nanoclusters (NCs) are promising catalytic materials for the electrochemical CO 2 reduction reaction (CO 2 RR). In this work an atomic level modification of a Au 23 NC is made by substituting two surface Au atoms with two Cd atoms, and it enhances the CO 2 RR selectivity to 90–95 % at the applied potential between -0.5 to -0.9 V, which is doubled compared to that of the undoped Au 23 . Additionally, the Cd-doped Au 19 Cd 2 exhibits the highest CO 2 RR activity (2200 mA mg -1 at -1.0 V vs. RHE) among the reported NCs. This synergetic effect between Au and Cd is remarkable. Density-functional theory calculations reveal that the exposure of a sulfur active site upon partial ligand removal provides an energetically feasible CO 2 RR pathway. The thermodynamic energy barrier for CO formation is 0.74 eV lower on Au 19 Cd 2 than on Au 23 . Here these results reveal that Cd doping can boost the CO 2 RR performance of Au NCs by modifying the surface geometry and electronic structure, which further changes the intermediate binding energy. This work offers insights into the surface doping mechanism of the CO 2 RR and bimetallic synergism.

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

Proton and neutron density distributions at supranormal density in low- and medium-energy heavy-ion collisions. II. Central Pb + Pb collisions

This paper represents a continuation of our investigation into the limitations on total, proton, and neutron particle number densities, as well as the asymmetry of proton and neutron density distributions achievable in central heavy-ion collisions. We explore these aspects at low and medium energies within the framework of the Boltzmann-Uhlenbeck-Uehling (pBUU) transport and time-dependent Hartree-Fock (TDHF) models. Previous studies, focusing on symmetric and asymmetric collisions of Ca and Sn nuclei [1], and initial results on Pb-nuclei collisions [2], emphasized the role of the Coulomb interaction in these events. Our findings indicated that: (i) the highest total densities predicted at 𝐸 beam = 800 MeV/nucleon were on the order of ≈ 2.5⁢𝜌 0 (𝜌 0 = 0.16 fm −3 ), (ii) the proton-neutron asymmetry for maximal densities, 𝛿=(𝜌$^{max}_{n}$− 𝜌$^{max}_{p}$)/(𝜌$^{max}_{n}$+𝜌$^{max}_{p}$), did not generally exceed the asymmetry in the initial state of the collision at all beam energies and tended to decrease during the reaction, and (iii) a significant portion of this asymmetry had its microscopic origin in Coulomb forces, masking the pure nuclear contribution. These new findings, particularly relevant in the astrophysical context, are further examined in this work, focusing on the heaviest target-projectile combination 212,208 Pb accessible in an experiment. We introduce the SkT3 Skyrme force model, not previously used for the Pb system, and compare it to the SV-bas and SV-sym34 models to explore the symmetry-energy dependence of the results. Contour plots of nucleonic densities are presented, contrasting the time evolution of the density distributions in low (TDHF) and high (pBUU) models. We also present the evolution of normalized maximal proton, neutron, and total nucleon number density with increasing beam energy in the full pBUU model and the Vlasov approximation, aiming to explore the impact of correlations in the reaction. The time evolution of the proton and neutron density distributions in the plane transverse to the beam direction is illustrated at both low and high beam energy. In conclusion, our detailed examination of the Pb system in this work provides further essential evidence that the aforementioned findings (i)–(iii) are only weakly dependent on system size and a symmetry-energy model, and thus, they are of more general importance.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Evaluation of Sandia NCS Benchmark Suite Updates

The Sandia Nuclear Criticality Safety (NCS) program’s benchmark suite was recently updated. This suite is used to ensure that NCS calculations using computer-based neutron transportation codes have an established baseline comparison of calculated versus known experimental results. The Evaluated Nuclear Data File (ENDF) version used for the MCNP models in the suite was changed from ENDF/B-VII.1 to ENDF/B-VIII.0. Additionally, relevant thermal scattering law data libraries (TSLs) were updated. The sensitivity of the calculational bias of each benchmark model to these changes is discussed. Implementation of the ENDF/B-VIII.0 library and updated TSLs results in improvements to bias distribution in the intermediate enriched uranium, plutonium, and mixed uranium–plutonium (IEU, PU, and MIX) fissionable material benchmark categories, but a small bias increase in low- and high-enriched uranium categories (LEU and HEU, respectively). The results also highlight the sensitivity of the benchmarks, with average lethargy of neutrons causing fission energies (EALF) in the intermediate energy range to ENDF/B library changes. The most numerous bias changes were observed in the thermal energy region when transitioning from ENDF/B-VII.1 to ENDF/B-VIII.0. In conclusion, most of the unique bias changes observed in MCNP 6.3.0 between the two nuclear data libraries were in the LEU-COMP-THERM evaluation subset.

ICSBEP↗
DOE OSTI2025

Scaling microstructural processes in the sintering of ionic ceramics

A multi-scale framework, combining a multiphase field formulation and large deformation mechanics, was developed as a stepping stone to perform the data analytics of the microstructural level kinetics of a sintering solid. Relevant microstructural information from this framework, such as grain, stress, and porosity statistics, was scaled up to describe the macroscopic level sintering kinetics. Here, the developed formulation was applied to describe the electric field assisted sintering of Y 2 O 3 . Microstructural inhomogeneities in a multi-granular solid result in the formation of a field of compressive stress networks, which interleave with low compression and weakly tensile regions, defining a scaffolding for sintering concentration regions to develop. A Poisson effect-induced lateral stress network is also naturally self-induced as a result of the mechanical constraints imposed by the sintering apparatus. For long sintering times, localized shear stresses enhancing mass flow along grain boundaries and internal surfaces develop. Three-sided pores are removed by either vacancy transport to the surrounding pores, or move towards the external surfaces through grain boundary diffusion. Four- and higher order-sided pores stabilize because an equal amount of vacancies are gained and lost through the connecting grain boundaries. Grain dewetting contributes to pore coalescence, suggesting that pore kinetics and grain growth are coupled and should be analyzed in concert. The combined sintering and grain growth kinetics define six regimes of sintering behavior: (1) T, the transient regime; (2) E$_Υ$, the surface energy dominated, early sintering regime, where the grain growth exponent, p = 1, and the stress concentration factor, $f$ ~ $1/\hat{ρ}^{4.6}$; (3) E S , the stress dominated, early sintering regime, where p = 1 and $f$ ~ $1/\hat{ρ}^{4}$; (4) I$_Υ$, the surface energy dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4.6}$; (5) I S , the stress dominated, intermediate sintering regime, where p = 2 and $f$ ~ $1/\hat{ρ}^{4}$; and (6) L, the late sintering regime, where p = 3 and $f$ ~ 1. At the macroscopic level, the rapid densification and suppression of grain growth observed in the electric field assisted sintering process is a consequence of the compounding effects of the underlying stress-, transport-, and interfacial-energy-induced energy minimization kinetics, as predicted by the multi-scale framework.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Heavy-ion fusion cross section formula and barrier height distribution

Methods for obtaining fusion cross section formulas are discussed, especially for those that take on an empirical form. A new expression starting with σ( E) = $\frac{1}{E}$ $\int ^{E}_{E_0}$ $(\int^{E'}_{E_0} B (E^\shortparallel) dE^\shortparallel)dE'$ has been explored. Here, B(E) is a reasonable, assumed function of the barrier height distribution, $\frac{d^2 (\sigma E)}{dE^2}$. Further, the resulting analytic cross section formula reproduces very well the excitation functions for many light and heavy fusion systems across wide energy ranges, when B(E) is assumed to be a multi-Gaussian function. This study offers an improved determination of the fusion barrier height distribution over other numerical techniques.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Merging of transport theory with the time-dependent Hartree-Fock approach: Multinucleon transfer in U + U collisions

Multinucleon transfer mechanism in the collision of 238 U + 238 U system is investigated at E c.m. = 833 MeV in the framework of the quantal diffusion description based on the stochastic mean-field approach. Double cross sections σ (N, Z ) as a function of the neutron and proton numbers, the cross sections σ (Z ) and σ (A) as a function of the atomic numbers and the mass numbers are calculated for production of the primary fragments. The calculation indicates the 238 U + 238 U system may be located at an unstable equilibrium state at the potential energy surface with a slightly negative curvature along the β stability line on the (N, Z ) plane. Here, this behavior may lead to rather large diffusion along the β stability direction.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

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

Imprints of high-momentum nucleons in nuclei on hard photons from heavy-ion collisions near the Fermi energy

The short-range correlation (SRC) induced by the tensor force in the isosinglet neutron-proton interaction channel leads to a high-momentum tail (HMT) in the single-nucleon momentum distributions n(k) in nuclei. Owing to the remaining uncertainties about the tensor force, the shape of the nucleon HMT may be significantly different from the dilute interacting Fermi gas model prediction n(k) ~ 1/k 4 similar to the HMT in cold atoms near the unitary limit. Within an isospin- and momentum-dependent Boltzmann-Uehling-Uhlenbeck transport model incorporating approximately the nucleon HMT, we investigate hard photon emissions in 14 N + 12 C and 48 Ca + 124 Sn reactions at beam energies around the Fermi energy. Imprints of different shapes of the HMT on the energy spectrum, angular distribution and transverse momentum spectrum of hard photons are studied. Furthermore, while the angular distribution does not carry any information about the shape of the nucleon HMT, the energy spectra and especially the mid-rapidity transverse momentum spectra of hard photons are found to bare strong imprints of the shapes of nucleon HMTs in the two colliding nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Reconceptualizing the Ir III Role in Metallaphotoredox Catalysis: From Strong Photooxidant to Potent Energy Donor

Dual Ir III /L n Ni II metallaphotoredox catalyzed C(sp 3 )–C(sp 2 ) cross-coupling reactions are widely assumed to proceed by photoinduced single electron transfer steps due to the highly oxidizing Ir III * excited state (Ir III = [Ir(dF(CF 3 )ppy) 2 (dtbbpy)] + [PF 6 ] – ; dF(CF 3 )ppy = 2-(2,4-difluorophenyl)-5-(trifluoromethyl)pyridine; L n = dtbbpy = 4,4'-di-tert-butyl-2,2'-bipyridine). Using time-resolved absorption and emission spectroscopy, we reveal that energy transfer between Ir III * and various LnNi II precatalysts and intermediates with k q ≥ 10 8 M –1 s –1 also drives catalysis. Specifically, the excited states of L n Ni II dihalide precatalysts/organometallic intermediates accessible by energy transfer appear to drive bond homolysis, halogen radical elimination, and reductive elimination reactions that facilitate formation of cross-coupled products. Energy transfer dynamics consequently circumvent the need for photoinduced electron transfer, thereby extending substrate scopes to coupling partners that cannot be oxidized by Ir III *. Within a cross-electrophile coupling model reaction between 4-bromobenzotrifluoride and bromocyclohexane, energy transfer activates the L n Ni II precatalyst at early reaction times before nucleophilic reductants are present. In the absence of Ir III , direct excitation of L n Ni II (Br) 2 also activates the precatalyst to form a L n Ni II (Br)(Aryl) intermediate. To compare energy transfer and electron transfer kinetics, we determined rate constants for reductive quenching by Br – (k SET = 4.1 × 10 8 M –1 s –1 ) and for the subsequent electron transfer from reduced Ir III•– to L n Ni II (Br) 2 (k SET = 4.1 × 10 7 M –1 s –1 ) using Stern-Volmer analysis and pulse radiolysis, respectively. Energy transfer rate constants are competitive with the electron transfer rate constants and energy transfer is a parallel pathway within metallaphotoredox catalysis. Exploiting the energy transfer mechanism, we demonstrate highly selective cross-electrophile coupling between 4-chlorobenzotrifluoride and bromocyclohexane to form exclusively cross-coupled product. Here, with alkyl-trifluoroborate nucleophiles that do not reductively quench IrIII* emission, transmetalation with L n Ni II (Br/Cl)(Aryl) followed by energy transfer also drives excited state reductive elimination to form C(sp 3 )–C(sp 2 ) cross-coupled product. Similarly, energy transfer rather than Ni II oxidation drives C(sp 2 )–OR reductive elimination, despite the strongly oxidizing ability of Ir III *. In total, these reactions demonstrate energy transfer processes from Ir III * to L n Ni II in metallaphotoredox catalysis that can unlock alternative reactive pathways.

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

Desulfatiglans anilini Initiates Degradation of Aniline With the Production of Phenylphosphoamidate and 4-Aminobenzoate as Intermediates Through Synthases and Carboxylases From Different Gene Clusters

The anaerobic degradation of aniline was studied in the sulfate-reducing bacterium Desulfatiglans anilini. Our aim was to identify the genes and their proteins that are required for the initial activation of aniline as well as to characterize intermediates of this reaction. Aniline-induced genes were revealed by comparison of the proteomes of D. anilini grown with different substrates (aniline, 4- aminobenzoate, phenol, and benzoate). Most genes encoding proteins that were highly abundant in aniline- or 4-aminobenzoate-grown D. anilini cells but not in phenol- or benzoate-grown cells were located in the putative gene clusters ani (aniline degradation), hcr (4-hydroxybenzoyl-CoA reductase) and phe (phenol degradation). Of these putative gene clusters, only the phe gene cluster has been studied previously. Based on the differential proteome analysis, four candidate genes coding for kinase subunits and carboxylase subunits were suspected to be responsible for the initial conversion of aniline to 4-aminobenzoate. These genes were cloned and overproduced in E. coli. The recombinant proteins were obtained in inclusion bodies but could be refolded successfully. Two subunits of phenylphosphoamidate synthase and two carboxylase subunits converted aniline to 4-aminobenzoate with phenylphosphoamidate as intermediate under consumption of ATP. Only when both carboxylase subunits, one from gene cluster ani and the other from gene cluster phe, were combined, phenylphosphoamidate was converted to 4-aminobenzoate in vitro, with Mn 2+ , K + , and FMN as co-factors. Thus, aniline is degraded by the anaerobic bacterium D. anilini only by recruiting genes for the enzymatic machinery from different gene clusters. We conclude, that D. anilini carboxylates aniline to 4-aminobenzoate via phenylphosphoamidate as an energy rich intermediate analogous to the degradation of phenol to 4-hydroxybenzoate via phenylphosphate.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Enhanced dynamics in fusion of neutron-rich oxygen nuclei at above-barrier energies

Above-barrier fusion cross sections for an isotopic chain of oxygen isotopes with A = 16 –19 incident on a C 12 target are presented. Experimental data are compared with both static and dynamical microscopic calculations. Here, these calculations are unable to explain the ≈ 37 % increase in the average above-barrier fusion cross section observed for O 19 as compared to β -stable oxygen isotopes. This result suggests that for neutron-rich nuclei existing time-dependent Hartree-Fock calculations underpredict the role of dynamics at near-barrier energies. High-quality measurement of above-barrier fusion for an isotopic chain of increasingly neutron-rich nuclei offers an effective means to probe this fusion dynamics.

6 ≤ A ≤ 19↗
DOE OSTI2022

Investigating effects of relativistic kinematics, dimensionality, interactions, and short-range correlations on the ratio of quartic over quadratic nuclear symmetry energies

While ample evidence for the so-called empirical parabolic law of the Equation of State (EOS) of isospin asymmetric nuclear matter (ANM) has been obtained in many studies within both non-relativistic and relativistic nuclear many-body theories using various interactions, it has been unclear if there is any fundamental physics reason for the small quartic symmetry energy compared to the quadratic one even as the ANM approaches pure neutron matter. Within both relativistic and non-relativistic Free Fermi Gas (FFG) models in coordinate spaces of arbitrary dimension d with and without considering Short-Range Correlations (SRC) as well as non-linear Relativistic Mean Field (RMF) models, we study effects of relativistic kinematics, dimensionality, interactions and SRC on the ratio Ψ(ρ) of quartic over quadratic symmetry energies in ANM EOSs. We found that the ratio Ψ(ρ) in the FFG model depends strongly on the dimension d. While it is very small already in the normal 3D space, it could be even smaller in spaces with reduced dimensions for sub-systems of particles in heavy-ion reactions and/or whole neutron stars due to constraints, collectivities and/or symmetries. Here, we also found that the ratio Ψ(ρ) could theoretically become very large only at the ultra-relativistic limit far above the density reachable in neutron stars. On the other hand, nuclear interaction directly and/or indirectly through SRC-induced high-momentum nucleons affect significantly the density dependence of Ψ(ρ) compared to the relativistic FFG model prediction. The SRC affects significantly not only the kinetic energy of symmetric nuclear matter but also the ratio Ψ(ρ) while the relativistic corrections are found negligible. The results may help better understand the EOS of dense neutron-rich matter.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Experimental investigation of abnormal transverse flow enhancement of α particles in heavy-ion collisions

The mass dependence of the transverse flow for Z = 1–5 fragments from the collisions of 40 Ar + 27 Al, 40 Ar + 48 Ti, and 40 Ar + 58 Ni at 47 MeV/nucleon is investigated experimentally in this article. The transverse flow values are determined using the in-plane components of the fragment transverse momenta, where three conventional methods, i.e., the kinetic flow tensor method, the transverse momentum analysis method, and the azimuthal correlation method, are applied to reconstruct the reaction plane in an event-by-event basis. It is demonstrated from the comparison of the present experimental mass dependent flow measurements and the model simulations using an improved antisymmetrized molecular dynamics model that the experimentally observed abnormal α transverse flow enhancement is closely related to the reaction plane reconstruction procedure in the flow extraction. We further investigate the physical existence of the abnormal α flow behavior using a two-particle azimuthal correlation method, which allows us to provide the relative flow magnitude information with an identification of fragment charge number without the knowledge of the reaction plane differing from the three conventional methods. It is found that the relative flow magnitudes deduced from the two-particle azimuthal correlation functions with an identification of Z, with the correction for the recoil effect imposed by the momentum conservation, show a monotonically increasing trend as a function of fragment charge number, with no exception of the α flow enhancement. These results, in addition to those from the improved antisymmetrized molecular dynamics model simulations, definitely provide experimental evidences for the inexistence of the abnormal α flow behavior in the heavy-ion collisions at the present incident energy region in nature.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Study of Quasielastic Barrier Distributions as a Step towards the Synthesis of Superheavy Elements with Hot Fusion Reactions

The excitation functions for quasielastic scattering of Ne 22 + Cm 248 , Mg 26 + Cm 248 , and Ca 48 + U 238 are measured using a gas-filled recoil ion separator. The quasielastic barrier distributions are extracted for these systems and are compared with coupled-channel calculations. The results indicate that the barrier distribution is affected dominantly by deformation of the actinide target nuclei, but also by vibrational or rotational excitations of the projectile nuclei, as well as neutron transfer processes before capture. From a comparison between the experimental barrier distributions and the evaporation residue cross sections for Sg ( Z = 106 ), Hs (108), Cn (112), and Lv (116), it is suggested that the hot fusion reactions take advantage of a compact collision, where the projectile approaches along the short axis of a prolately deformed nucleus. Overall, a new method is proposed to estimate the optimum incident energy to synthesize unknown superheavy nuclei using the barrier distribution.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Unraveling the CO Oxidation Mechanism over Highly Dispersed Pt Single Atom on Anatase TiO 2 (101)

Catalysts with noble metals deposited as single atoms on metal oxide supports have recently been studied extensively due to their maximized metal utilization and potential for performing difficult chemical conversions owing to their unique electronic properties. Understanding of the reaction mechanisms on supported single-metal atoms is still limited but is highly important for designing more efficient catalysts. In this study, we report the complexity of the CO oxidation reaction mechanism on Pt single atoms supported on anatase TiO 2 (Pt SA /a-TiO 2 ) by coupling density functional theory (DFT) calculations and microkinetic analysis with kinetic measurements, in situ/operando infrared, and X-ray absorption spectroscopies. Starting from the adsorbed Pt SA occupying an O vacancy induced by reductive pretreatment, we show that CO oxidation follows a complex mechanism consisting of initiation steps to reorganize the active site and multibranch reactive cycles, with the Pt SA /a-TiO 2 catalyst not returning to its initial configuration. The initiation step consists of CO and O 2 adsorption healing the O vacancy, followed by CO oxidation using gas-phase CO to form Pt(CO). The reactive cycle alternates O 2 adsorption and dissociation to oxidize the catalyst to Pt(O)(O)(CO) and branching pathways of competing Langmuir–Hinshelwood (LH)- or Eley–Rideal (ER)-type CO oxidation steps to reduce it again to Pt(CO). In situ/operando infrared experiments, including cryogenic CO adsorption and isotopic CO exchange, confirm the combined involvement of strongly adsorbed CO and gas-phase CO in an Eley–Rideal step along the reaction cycle. Microkinetic modeling shows that Pt single atoms are present in a mixture of Pt(CO), Pt(CO)(O 2 ), Pt(O)(CO)(O 2 ), and Pt(CO)(CO 3 ) structures as the main intermediates during steady-state CO oxidation, all having the C–O vibrational stretch close to the experimentally observed value of 2115 cm –1 . Microkinetic modeling also shows that the fractional orders of CO and O 2 measured experimentally originate from multiple steps with a high degree of rate control and not from a simple competitive adsorption. The results demonstrate the complex reaction pathways that even CO oxidation on a simple single-atom system can follow, providing mechanistic insights for designing efficient Pt-based single-atom catalysts. Here, we further show that microkinetic modeling results are sensitive to changes in energies of intermediate and transition states within errors of density functional theory, which can ultimately lead to incorrect conclusions regarding the reaction pathways and most abundant reaction intermediates if not accounted for by experiments.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Calculation of the C 12 + C 12 sub-barrier fusion cross section in an imaginary-time-dependent mean field theory

The 12 C + 12 C sub-barrier fusion cross section is calculated within the framework of a time-dependent Hartree-Fock-based classical model using the Feynman path-integral method. The modified astrophysical S* factor is compared to direct and indirect experimental results. A good agreement with the direct data is found. In the lower-energy region where recent analyses of experimental data obtained with the Trojan horse method (THM) lead to contrasting results, the model predicts a nonresonant S* factor half-way between those results. Low-energy resonances revealed in the THM data are added to the calculation, and the relative reaction rate in the Gamow region is calculated. In particular, including 0 + resonances result in some agreement with the THM data. Here, the role of different resonances is discussed in detail, and their influence on the reaction rate at temperatures relevant to stellar evolution is investigated.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

Production of neutron-rich isotopes for 𝑍 ≥ 98 in the 238 U + 248 Cm reaction

Multinucleon transfer (MNT) reactions in actinide systems are a promising method to synthesize transuranium neutron-rich elements. Appropriate theoretical approaches are needed to understand the mechanisms behind MNT. We employ a microscopic approach to calculate neutron-rich isotope production in the reaction 238 U + 248 Cm system. Here, the stochastic mean-field (SMF) approach is used to calculate the primary cross sections in MNT reactions based on the quasifission and inverse quasifission processes, and a statistical de-excitation model with GEMINI ++ code to calculate the secondary fragment cross sections. The calculated cross sections using SMF and GEMINI ++ explain available experimental results for the 238 U + 248 Cm system at 𝐸 c.m. = 898.7 MeV energy. This shows the effectiveness and applicability of the quantal diffusion approach, based on the SMF theory, in heavy-ion collisions. Production of transuranium neutron-rich elements with a proton number up to 𝑍=101 is obtained with sizable cross sections. Theoretical results calculated for the 𝑍=102–105 region, for which there are no experimental data, show that the cross-section values would be lower than the microbarn level. SMF theory does not contain any adjustable parameters other than the standard parameters of the energy density functional used in the TDHF theory and is an important approach for the microscopic understanding of reaction mechanisms.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗