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At least 163 records · Page 9

The cross-section measurement for the 3 H($e, e'K^+)nnΛ$ reaction

The small binding energy of the hypertriton leads to predictions of the non-existence of bound hypernuclei for isotriplet three-body systems such as nnΛ. However, invariant mass spectroscopy at GSI has reported events that may be interpreted as the bound nnΛ state. The nnΛ state was sought by missing-mass spectroscopy via the (e, e'K + ) reaction at Jefferson Lab’s experimental Hall A. The present experiment has higher sensitivity to the nnΛ-state investigation in terms of better precision by a factor of about three. The analysis shown in this article focuses on the derivation of the reaction cross-section for the 3 H(γ*, K + )X reaction. Events that were detected in an acceptance, where a Monte Carlo simulation could reproduce the data well (|δp/p| < 4%), were analyzed to minimize the systematic uncertainty. No significant structures were observed with the acceptance cuts, and the upper limits of the production cross-section of the nnΛ state were obtained to be 21 and $31 nbsr -1 at the 90% confidence level when theoretical predictions of (-B Λ , Γ) = (0.25, 0.8) MeV and (0.55, 4.7) MeV, respectively, were assumed. The cross-section result provides valuable information for examining the existence of nnΛ.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Cumulative short-lived photofission product yields for nuclear forensic application

Experiments have long been carried out with linear accelerator (linac) produced bremsstrahlung X-rays to study high-energy photon-induced fission, known as “photofission”. One benefit of photofission, when compared with neutron-induced fission, is the ability to investigate fundamental physics of fission at excitation energies lower than what is possible with neutrons [1]. Absorption of an incident neutron results in a compound nucleus with an excitation energy at least equal to the neutron binding energy; thus, the lowest energy region of the fission barrier cannot be studied. Fission product yield distributions are dependent on the incident particle energy and the target nucleus mass. They are generally represented by a double-humped curve, with low and high mass “peaks” and an intermediate mass “valley”. As incident particle energy increases, the excitation energy of the nucleus increases, thereby increasing the overall yield of isotopes in the valley with respect to the two maxima or peaks of the fission product curve [3]. Photofission is most probable for incident photons around 14 MeV due to the giant dipole resonance. Induced photofission around this energy results in a fission product yield distribution that resembles 14 MeV DT neutron fission more than thermal or fast (500 keV) neutron fission. In post-detonation nuclear forensics, the peak-to-valley ratio of the fission product yield curve could be used for characterizing device type by providing an indication of the neutron energy spectrum that had induced fission (e.g., 500 keV vs. 14 MeV). The goal of this work is to improve nuclear data for isotopes of interest in nuclear forensics and special nuclear material (SNM) detection, specifically the fission product yield data via photofission experiments for the isotopes of 238U and 232Th. Photofission has been proposed as a less costly and more flexible production method for the valley isotopes that are representative of DT neutron fission product yield distributions, which would benefit nuclear forensics exercises in testing for analysis techniques. Natural uranium and thorium targets were irradiated with bremsstrahlung photons (nominal endpoint energies of 8, 14, and 20 MeV), generated via impingement of high-energy electrons on a tungsten electron-to-photon radiator. Gamma-ray spectroscopy was used to observe and identify the decay of the resulting fission products. The photofission yields of 102 fission products were measured for the set of the 238U and 232Th targets at the three bremsstrahlung X-ray endpoint energies 8, 14, and 20 MeV. These fragments included masses ranging from A=84 to A=144, with half-lives as short as 1.07 seconds.

07 ISOTOPE AND RADIATION SOURCES↗

Radio AGN in nearby dwarf galaxies: the important role of AGN in dwarf galaxy evolution

ABSTRACT We combine deep optical and radio data, from the Hyper Suprime-Cam and the Low-Frequency Array (LOFAR), respectively, to study 78 radio active galactic nuclei (AGN) in nearby (z < 0.5) dwarf galaxies. Comparison to a control sample, matched in stellar mass and redshift, indicates that the AGN and controls reside in similar environments, show similar star formation rates (which trace gas availability) and exhibit a comparable incidence of tidal features (which indicate recent interactions). We explore the AGN properties by combining the predicted gas conditions in dwarfs from a cosmological hydrodynamical simulation with a Monte Carlo suite of simulated radio sources, based on a semi-analytical model for radio-galaxy evolution. In the subset of LOFAR-detectable simulated sources, which have a similar distribution of radio luminosities as our observed AGN, the median jet powers, ages, and accretion rates are ∼1035 W, ∼5 Myr, and ∼10−3.4 M⊙ yr−1, respectively. The median mechanical energy output of these sources is ∼100 times larger than the median binding energy expected in dwarf gas reservoirs, making AGN feedback plausible. Since special circumstances (in terms of environment, gas availability, and interactions) are not necessary for the presence of AGN, and the central gas masses are predicted to be an order of magnitude larger than that required to fuel the AGN, AGN triggering in dwarfs is likely to be stochastic and a common phenomenon. Together with the plausibility of energetic feedback, this suggests that AGN could be important drivers of dwarf galaxy evolution, as is the case in massive galaxies.

Davis, F. (ORCID:0000000285224980)↗

Local position-space two-nucleon potentials from leading to fourth order of chiral effective field theory

We present local, position-space chiral NN potentials through four orders of chiral effective field theory ranging from leading order (LO) to next-to-next-to-next-to-leading order (N 3 LO, fourth order) of the Δ-less version of the theory. The long-range parts of these potentials are fixed by the very accurate πN LECs as determined in the Roy-Steiner equations analysis. At the highest order (N 3 LO), the NN data below 190 MeV laboratory energy are reproduced with the respectable χ 2 /datum of 1.45. A comparison of the N 3 LO potential with the phenomenological Argonne v 18 (AV18) potential reveals substantial agreement between the two potentials in the intermediate range ruled by chiral symmetry, thus, providing a chiral underpinning for the phenomenological AV18 potential. Our chiral NN potentials may serve as a solid basis for systematic ab initio calculations of nuclear structure and reactions that allow for a comprehensive error analysis. In particular, the order by order development of the potentials will make possible a reliable determination of the truncation error at each order. Our new family of local position-space potentials differs from existing potentials of this kind by a weaker tensor force as reflected in relatively low D-state probabilities of the deuteron (P D ≲ 4.0 % for our N 3 LO potentials) and predictions for the triton binding energy above 8.00 MeV (from two-body forces alone). As a consequence, our potentials may lead to different predictions when applied to light and intermediate-mass nuclei in ab initio calculations and, potentially, help solve some of the outstanding problems in microscopic nuclear structure.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Elemental Fractionation During Rapid Accretion of the Moon Triggered by a Giant Impact

Recently, Ida et al. made an N-body simulation of lunar accretion from a protolunar disk formed by a giant impact. One of their important conclusions is that the accretion time of the Moon is as short as one month. Such rapid accretion is a necessary consequence of the high surface density of a lunar mass disk accreting just beyond the Roche limit (about 3Re); the Safronov accretion time (a few days) is even shorter. The energy of accretion always exceeds the gravitational binding energy of newly arriving matter. Hence, without an energy sink, the accreting body is thermally unstable. For the Earth and other planets, radiation acts as the sink. However, in such a short accretion time, the Moon cannot radiate the accretional energy. Even radiating at a silicate cloudtop temperature of roughly 2000 K, it would take more than 100 yr to radiatively cool the Moon. The plausible alternative heat sinks are heat capacity, latent heat of vaporization, and thermal escape of the gas to space (i.e., hydrodynamic blowoff). The latter becomes plausible for the Moon because the scale height at 2000 K (about 300 km) is a significant fraction of the lunar radius. The early stages of lunar (or "lunatesimal") growth release relatively little energy and can occur simply by heating the material, especially if the accreting material is originally cold. However, the material is unlikely to be cold, because the disk itself is hot and cooling time is long, while the lunar accretion time iss very short. Therefore, the moon is likely to accrete condensed material just after it condenses. Accordingly, the newly accreted material will be on the verge of vaporization and will have very little heat capacity to spare. The immediate heat sink is the latent heat of vaporization. Most of the vapor will escape from the moon, because the thermal energy in the gas can be used to drive escape. However, vaporization is generally incomplete. the latent heat of vaporization exceeds the energy of accretion. Viewed globally, the accretional energy is about half the energy required to vaporize the entire Moon. Thus to first approximation, half of the Moon-forming material can be vaporized and lost during accretion. During this process, we would expect preferential loss of relatively volatile elements. Escape will retard the rate of accretion. To test these ideas, we computed detailed models of the thermal state of the Moon during accretion. We pay special attention to the structure of the silicate atmosphere and its loss rate by calculating the chemical species at equilibrium. We used the PHEQ program which includes 12 elements (H,O,C,Mg,Si,Fe,Ca, Al, Na,Ti, and N.) and 272 compounds (including ionic compounds). Because of the large heats of vaporization and ionization, the adiabatic atmosphere is nearly isothermal and massive escape is expected. The pressure of the atmosphere is determined by the balance between vaporization of a accreting material and escape. If the accretion time is one month, a 0.3 bar atmosphere is expected. Elemental fractionation depends strongly on the temperature of the accreting material. The initial temperature of the material can be estimated from the condition of gravitational instability in the protolunar disk. As shown by Ida et al, accretion starts when gravitational instability occurs when more than 99% of the material condenses. At this point, all of Ca, Al, Si, Mg, and Fe, and 95% of Na (probably K also), are in condensed phases. If the moon is formed from the accretion of such material, volatile elements such as Na, and K are retained by the moon only early in accretion. At later times, K and Na are lost and a fraction of the MG, Si and Fe is lost. However, refractory elements such as Ca and Al are retained and so achieve a mild degree (factor 2) of superabundance.

Abe, Y.↗

Construction of a Pt‐CeO x Interface for the Electrocatalytic Hydrogen Evolution Reaction

Abstract The creation of metal‐metal oxide interfaces is an important approach to fine‐tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeO x that improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt‐CeO x interfaces are formed by depositing size‐controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeO x nanosheets. This interface structure facilitates substantial electron transfer from Pt to CeO x , resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt‐CeO x interfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.

25 ENERGY STORAGE↗

The physics of grain-grain collisions and gas-grain sputtering in interstellar shocks

Grain-grain collisions and ion sputtering destroy dust grains in interstellar shocks. An analytical theory is developed for the propagation of shock waves in solids driven by grain-grain collisions, which compares very favorably with detailed numerical calculations. This theory is used to determine the fraction of grain vaporized by a grain-grain collision. Our results predict much less vaporization of colliding grains in interstellar shocks than previous estimates. This theory can also be used to determine the fraction of a colliding grain that melts, shatter, or undergoes a phase transformation to a higher density phase. In particular, the latter two processes can be much more important in interstellar shocks than vaporization. The sputtering of grains by impacting gas ions is reanalyzed based upon extensive laboratory studies and a theoretically derived 'universal'sputtering relation. The analytical results are compared to available experimental studies of sputtering of graphite/amorphous carbon, SiO2, SiC, Fe, and H2O. Sputtering yields for astrophysically relevant materials as a function of impact energy and ion mass are derived. These yields are also averaged over thermal impact spectrum and simple polynomial fits to the resulting yields as a function of temperature are presented. The derived sputtering yields are similar to those adopted in previous studies, except for graphite near threshold where the new yields are much larger due to a lower adopted binding energy. The ion bombardment will amorphitize the surface layers of interstellar grains. It will also convert graphite into hydrogenated amorphous carbon (HAC) to a depth of 10-20 A. It is suggested that these HAC surfaces are the carriers of the 3.4 micrometer absorption feature in the interstellar medium.

Tielens, A. G. G. M.↗

Low-energy calibration of SuperCDMS HVeV cryogenic silicon calorimeters using Compton steps

Cryogenic calorimeters for low-mass dark matter searches have achieved sub-eV energy resolutions, driving advances in both low-energy calibration techniques and our understanding of detector physics. The energy deposition spectrum of gamma rays scattering off target materials exhibits step-like features, known as Compton steps, near the binding energies of atomic electrons. Here, we demonstrate a successful use of Compton steps for sub-keV calibration of cryogenic silicon calorimeters, utilizing four SuperCDMS High-Voltage eV-resolution detectors operated with 0 V bias across the crystal. This new calibration at 0 V is compared with the established high-voltage calibration using optical photons. The comparison indicates that the detector response at 0 V is about 30% weaker than expected, highlighting challenges in detector response modeling for low-mass dark matter searches.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

New calculation of the properties of the positronium ion

The positronium negative ion Ps(-), the system composed of two electrons and a positron, has been reinvestigated theoretically. Using a Hylleraas wave function with two nonlinear parameters and more than 200 linear terms, excellent values of binding energy and annihilation lifetime of the particle-stable 1Se ground state have been obtained. In addition, the question of stability of the 3Pe state discussed by Mills has been examined and it is agreed with his conclusion that the state is probably not stable against breakup into Ps(n = 2) + e(-). Improved limits on the critical 'positron' mass for binding the 3Pe state have also been obtained.

Bhatia, A. K.↗

Cosmic evolution of non-topological solitons, paper 1

Nontopological solitons are stable field configurations which may be formed in a primordial phase transition. Their cosmic evolution is studied, and the possibility that such objects could contribute significantly to the energy density of the Universe is examined. As the Universe cools, initially all but the largest lumps evaporate into free particles; those which survive may subsequently enter a brief accretion phase before they freeze out at a final size. Although the minimum critical charges which survive depend on particle masses and couplings, researchers develop an analysis which applies to a wide class of models. In most cases, solitons of moderate size survive the evaporation process only if there is a significant charge asymmetry or if they form at a temperature well below their binding energy per charge.

Frieman, Joshua A.↗

AI-Accelerated Design of Targeted Covalent Inhibitors for SARS-CoV-2

Direct-acting antivirals for the treatment of the COVID-19 pandemic caused by the SARS-CoV-2 virus are needed to complement vaccination efforts. Given the ongoing emergence of new variants, automated experimentation, and active learning based fast workflows for antiviral lead discovery remain critical to our ability to address the pandemic’s evolution in a timely manner. While several such pipelines have been introduced to discover candidates with noncovalent interactions with the main protease (M pro ), here we developed a closed-loop artificial intelligence pipeline to design electrophilic warhead-based covalent candidates. Here, this work introduces a deep learning-assisted automated computational workflow to introduce linkers and an electrophilic “warhead” to design covalent candidates and incorporates cutting-edge experimental techniques for validation. Using this process, promising candidates in the library were screened, and several potential hits were identified and tested experimentally using native mass spectrometry and fluorescence resonance energy transfer (FRET)-based screening assays. We identified four chloroacetamide-based covalent inhibitors of M pro with micromolar affinities (K I of 5.27 μM) using our pipeline. Experimentally resolved binding modes for each compound were determined using room-temperature X-ray crystallography, which is consistent with the predicted poses. The induced conformational changes based on molecular dynamics simulations further suggest that the dynamics may be an important factor to further improve selectivity, thereby effectively lowering KI and reducing toxicity. These results demonstrate the utility of our modular and data-driven approach for potent and selective covalent inhibitor discovery and provide a platform to apply it to other emerging targets.

60 APPLIED LIFE SCIENCES↗

Molecular Cooling as a Probe of Star Formation: Spitzer Looking Forward to Herschel

We explore here the question of how cloud physics can be more directly probed when one observes the majority of cooling emissions from molecular gas. For this purpose we use results from a recent Spitzer Space Telescope study of the young cluster of embedded objects in NGC1333. For this study we mapped the emission from eight pure H2 rotational lines, from S(0) to S(7). The H2 emission appears to be associated with the warm gas shocked by the multiple outflows present in the region. The H2 lines are found to contribute to 25 - 50% of the total outflow luminosity, and can be used to more directly ascertain the importance of star formation feedback on the natal cloud. From these lines, we determine the outflow mass loss rate and, indirectly, the stellar infall rate, the outflow momentum and the kinetic energy injected into the cloud over the embedded phase. The latter is found to exceed the binding energy of individual cores, suggesting that outflows could be the main mechanism for cores disruption. Given the recent launch of Herschel and the upcoming operational lifetime of SOFIA we discuss how studies of molecular cooling can take a step beyond understanding thermal balance to exploring the origin, receipt, and transfer of energy in atomic and molecular gas in a wide range of physical situations.

Bergin, Edwin A.↗

Compiled properties of nucleonic matter and nuclear and neutron star models from nonrelativistic and relativistic interactions

Here, this paper compiles the model parameters and zero-temperature properties of an extensive collection of published theoretical nuclear interactions, including 255 nonrelativistic (Skyrme-like) forces, 270 relativistic mean field (RMF) and point-coupling (RMF-PC) forces, and 13 Gogny-like forces. This forms the most exhaustive tabulation of model parameters to date. The properties of uniform symmetric matter and pure neutron matter at the saturation density are determined. Symmetry properties found from the second-order term of a Taylor expansion in neutron excess are compared with the energy difference of pure neutron and symmetric nuclear matter at the saturation density. Selected liquid-droplet model parameters, including the surface tension and surface symmetry energy, are determined for semi-infinite surfaces. Theoretical liquid droplet model neutron skin thicknesses of the neutron-rich closed-shell nuclei 48 Ca and 208 Pb are compared with published theoretical Hartree-Fock and experimental results. A similar comparison is made between theoretical liquid-droplet and experimental values of dipole polarizabilities. In addition, radii, binding energies, moments of inertia and tidal deformabilities of 1.2⁢M ⊙ , 1.4⁢M ⊙ and 1.6⁢M ⊙ neutron stars are computed. An extensive correlation analysis of bulk matter, nuclear structure, and low-mass neutron star properties is performed and compared with nuclear experiments and astrophysical observations.

nuclear astrophysics↗

Influence of counterion substitution on the properties of imidazolium-based ionic liquid clusters

Due to their unique physiochemical properties that may be tailored for specific purposes, ionic liquids (ILs) have been investigated for various applications, including chemical separations, catalysis, energy storage, and space propulsion. The different cations and anions comprising ILs may be selected to optimize a range of desired properties, such as thermal stability, ionic conductivity, and volatility, leading to the designation of certain ILs as designer “green” solvents. The effect of counterions on the properties of ILs is of both fundamental scientific interest and technological importance. Herein, we report a systematic experimental and theoretical investigation of the size, charge, stability toward dissociation, and geometric/electronic structure of 1-ethyl-3-methyl imidazolium (EMIM)-based IL clusters containing two different atomic counterions (i.e., bromide [Br − ] and iodide [I − ]). This work extends our studies of EMIM + cations with atomic chloride (Cl − ) and molecular tetrafluoroborate (BF 4 − ) anions reported previously by Baxter et al. [Chem. Mater. 34, 2612 (2022)] and Zhang et al . [J. Phys. Chem. Lett. 11, 6844 (2020)], respectively. Distributions of anionic IL clusters were generated in the gas phase using electrospray ionization and characterized by high mass resolution mass spectrometry, energy-resolved collision-induced dissociation, and negative ion photoelectron spectroscopy experiments. The experimental results reveal anion-dependent trends in the size distribution, relative abundance, ionic charge state, stability toward dissociation, and electron binding energies of the IL clusters. Complementary global optimization theory provides molecular-level insights into the bonding and electronic structure of a selected subset of clusters, including their low energy structures and electrostatic potential maps, and how these fundamental characteristics are influenced by anion substitution. Collectively, our findings demonstrate how the fundamental properties of ILs, which determine their suitability for many applications, may be tuned by substituting counterions. These observations are critical in the sub-nanometer cluster size regime where phenomena do not scale predictably to the bulk phase, and each atom counts toward determining behavior.

cluster↗

Cooperative Effects Drive Water Oxidation Catalysis in Cobalt Electrocatalysts through the Destabilization of Intermediates

A barrier to understanding the factors driving catalysis in the oxygen evolution reaction (OER) is understanding multiple over- lapping redox transitions in the OER catalysts. The complexity of these transitions obscure the relationship between the coverage of adsorbates and OER kinetics, leading to an experimental challenge in measuring activity descriptors, such as binding energies, as well as adsorbate interactions, which may destabilize intermediates and modulate their binding energies. Herein, we utilize a newly designed optical spectroelectrochemistry system to measure these phenomena in order to contrast the behavior of two electrocatalysts, cobalt oxyhydroxide (CoOOH) and cobalt-iron hexacyanoferrate (cobalt-iron Prussian blue, CoFe-PB). Three distinct optical spectra are observed in each catalyst, corresponding to three separate redox transitions, the last of which we show to be active for the OER using time-resolved spectroscopy and electrochemical mass spectroscopy. By combining predictions from density functional theory with parameters obtained from electroadsorption isotherms, we demonstrate that a destabilization of catalytic intermediates occurs with increasing coverage. In CoOOH, a strong (~0.34 eV/ monolayer) destabilization of a strongly bound catalytic intermediate is observed, leading to a potential offset between the accumulation of the intermediate and measurable O 2 evolution. We contrast these data to CoFe-PB, where catalytic intermediate generation and O 2 evolution onset coincide due to weaker binding and destabilization (~0.19 eV/monolayer). By considering a correlation between activation energy and binding strength, we suggest that such adsorbate driven destabilization may account for a significant fraction of the observed OER catalytic activity in both materials. Finally, we disentangle the effects of adsorbate interactions on state coverages and kinetics to show how adsorbate interactions determine the observed Tafel slopes. Crucially, the case of CoFe-PB shows that, even where interactions are weaker, adsorption remains non-Nernstian, which strongly influences the observed Tafel slope.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗

Corrosion-Resistant Non-Carbon Electrocatalyst Supports for PEFCS

Insufficient durability of commercial catalysts is a persistent issue for PEFC applications.1 Herein, Pt on Nb-doped-TiO 2 is reported as a highly durable electrocatalyst on which the direct 4-electron reduction of oxygen to water is more facile compared to Pt/C. All performance metrics are reported comparing Pt/Nb-TiO2 with a 15% Pt loading, against a commercial Pt/C catalyst (46.5% Pt loading, Tanaka, K. K.). Nb-doped-TiO 2 with high surface area and high electronic conductivity was synthesized using the supercritical fluid method. Initially, the durability of the catalyst was characterized using accelerated stability tests (ASTs) involving 10,000 high potential cycles (DOE/FCCJ protocol) and the Pt/Nb-TiO 2 was found to retain 78% of its initial electrochemically active surface area (ECSA) compared to the 57.6 % retained by Pt/C. These observations were in excellent agreement with previous reports that the Pt particle size of Pt/C grew from 2nm to 8nm during the AST protocol along with severe corrosion and amorphization of the carbon surface.2, 3 TEM and XPS studies of the Pt-Nb-doped-TiO 2 catalyst showed that the Pt particle size grew from 3nm to 6nm and the Nb(IV) and Ti(III) in the support were oxidized to Nb(V) and Ti(IV) after the durability test. Thus, the improvement in Pt/Nb-TiO 2 ECSA retention was attributed to the lower extent of particle growth and lack of oxidative support loss upon oxidation as compared to Pt/C. The oxygen reduction reaction (ORR) performance was characterized by linear polarization using a rotating disk electrode (RDE). The electrochemical surface areas of Pt/Nb-TiO 2 and Pt/C were found to be 48m2·g -1 and 83m2·g -1 respectively, and the mass activity for the ORR at 0.9V vs. RHE were found to be 150 mA·mg-1Pt and 124 mA·mg-1Pt respectively. The improved mass activity on Pt/Nb-TiO 2 was attributed to strong metal support interaction (SMSI) between the Nb-TiO 2 support and the Pt catalyst based on the 625 meV decrease in the binding energy of the Pt4f x-ray photo-electron spectroscopy (XPS) peaks of Pt/Nb-TiO 2 compared to Pt/C. To quantify the impact of the SMSI, a kinetic model was applied to calculate the elementary reaction rate constants for the various steps of the ORR on both catalysts. The reaction rate constant (k1) for the direct 4-electron transfer pathway to produce H 2 O was significantly larger in Pt/Nb-TiO 2 as compared to Pt/C. Thus, the reduction in the electron binding energy as observed in the XPS was found to aid the facile filling of the higher energy 2p orbitals of O 2 thereby leading to improved 4-electron transfer kinetics and improved overall activity.

08 HYDROGEN↗

Anomalous isotope effect on the optical bandgap in a monolayer transition metal dichalcogenide semiconductor

Isotope effects have received increasing attention in materials science and engineering because altering isotopes directly affects phonons, which can affect both thermal properties and optoelectronic properties of conventional semiconductors. However, how isotopic mass affects the optoelectronic properties in 2D semiconductors remains unclear because of measurement uncertainties resulting from sample heterogeneities. Here, we report an anomalous optical bandgap energy red shift of 13 (±7) milli–electron volts as mass of Mo isotopes is increased in laterally structured 100 MoS 2 - 92 MoS 2 monolayers grown by a two-step chemical vapor deposition that mitigates the effects of heterogeneities. This trend, which is opposite to that observed in conventional semiconductors, is explained by many-body perturbation and time-dependent density functional theories that reveal unusually large exciton binding energy renormalizations exceeding the ground-state renormalization energy due to strong coupling between confined excitons and phonons. The isotope effect on the optical bandgap reported here provides perspective on the important role of exciton-phonon coupling in the physical properties of two-dimensional materials.

36 MATERIALS SCIENCE↗