Electrocatalyst Design for Direct Borohydride Oxidation Guided by First Principles

© 2017 American Chemical Society. Density functional theory (DFT) calculations are used to propose a Au-Cu binary metal catalyst for the electrochemical borohydride oxidation reaction (BOR), which is evaluated experimentally and observed to show enhanced oxidation activity relative to a pure Au electrode. Our previous work has applied DFT methods to determine the BOR mechanism and elucidate the key reaction steps that dictate catalyst activity and selectivity to complete oxidation. A balanced initial adsorption strength of the borohydride anion is essential for an active and selective catalyst. Adsorption must be strong enough to provide a reasonable coverage of surface species and promote B-H bond dissociation but not so strong as to promote easy dissociation and provide a high coverage of surface H atoms that result in H 2 evolution. Borohydride adsorption energetics were evaluated for a series of close-packed pure metal surfaces. Copper catalysts appear encouraging but are not electrochemically stable under reaction conditions. Gold-copper alloys are predicted to show increased activity compared to a pure gold electrode while maintaining the selectivity to direct oxidation and increasing the stability compared to pure Cu. DFT results suggest an approximately 0.2 V decrease in the overpotential for borohydride oxidation on a Au 2 Cu(111) electrode compared to that on a Au(111) electrode. This DFT-predicted reduction in overpotential is realized experimentally. Electrodeposition was used to prepare AuCu electrodes, and their borohydride oxidation electrokinetics were examined by linear sweep voltammetry. An 88.5% gold and 11.5% copper sample demonstrated an overpotential reduction of 0.17 V compared to a pure Au electrode. The binding energy and adsorption free energy of BH 4- over other surface alloys are also examined to further identify promising BOR electrodes. (Chemical Equation Presented)

Thermodynamic modeling of the Pd-Zn system with uncertainty quantification and its implication to tailor catalysts

Pd-Zn intermetallic catalysts show encouraging combinations of activity and selectivity on well-defined active site ensembles. Thermodynamic description of the Pd-Zn system, delineating phase boundaries, and enumerating site occupancies within intermediate alloy phases, are essential to determining the ensembles of Pd-Zn atoms as a function of composition and temperature. Combining the present extensive first-principles calculations based on density functional theory (DFT) and available experimental data, the Pd-Zn system was remodeled using the CALculation of PHAse Diagrams (CALPHAD) approach. High throughput modeling tools with uncertainty quantification, i.e., ESPEI and PyCalphad, were incorporated in the phase analysis. The site occupancies across the {\gamma}-phase composition region were given special attention. A four-sublattice model was used for the {\gamma}-phase owing to its four Wyckoff positions, i.e., the outer tetrahedral (OT) site 8c, the inner tetrahedral (IT) site 8c, the octahedral (OH) 12e, and the cuboctahedral (CO) site 24g. The site fractions of Pd and Zn calculated from the present thermodynamic model show the occupancy preference of Pd in the OT and OH sublattices in agreement with experimental observations. The force constants obtained from DFT-based phonon calculations further supports the tendency of Pd occupying the OH sublattice compared with the IT and CO sublattice. The catalytic assembles changing from Pd monomers (Pd1) to trimers (Pd3) on the surface of the {\gamma}-phase is attributed to the increase of Pd occupancy in the OH sublattice.Comment: 12 figure

Examining the Relationship Between Schizotypy and Self-Reported Visual Imagery Vividness in Grapheme-Color Synaesthesia.

Synaesthesia is a condition in which one property of a stimulus triggers a secondary experience not typically associated with the first (e.g., seeing achromatic graphemes can evoke the perception of color). Recent work has explored a variety of cognitive and perceptual traits associated with synaesthesia. One example is in the domain of personality, where higher rates of positive schizotypy and openness to experience and lower agreeableness have been reported in synaesthetes who experience color as their evoked sensation relative to typical adult controls. Additionally, grapheme-color synaesthetes have previously been reported to show elevated mental imagery compared to typical adults. Here, we aimed to further elucidate the relationship between personality, synaesthesia, and other cognitive traits. In Study 1, we examined self-reported schizotypy and self-reported visual imagery vividness in grapheme-color synaesthetes and typical adults. Our results partially replicated previous findings by showing that synaesthesia was associated with greater positive schizotypy and enhanced self-reported imagery vividness. The results also extend previous reports by demonstrating that differences in positive schizotypy and mental imagery vividness are not related in grapheme-color synaesthesia. In Study 2, we sought to build on prior work showing lower agreeableness and increased openness to experience in synaesthetes by examining whether grapheme-color synaesthesia is associated with other conceptually related traits; namely lower self-monitoring and increased sensation seeking. We did not find any differences between synaesthetes and controls on either of these traits. These findings are discussed in relation to potential factors that may contribute to the observed personality profile in grapheme-color synaesthesia

The ReaxFF reactive force-field : development, applications and future directions

The reactive force-field (ReaxFF) interatomic potential is a powerful computational tool for exploring, developing and optimizing material properties. Methods based on the principles of quantum mechanics (QM), while offering valuable theoretical guidance at the electronic level, are often too computationally intense for simulations that consider the full dynamic evolution of a system. Alternatively, empirical interatomic potentials that are based on classical principles require significantly fewer computational resources, which enables simulations to better describe dynamic processes over longer timeframes and on larger scales. Such methods, however, typically require a predefined connectivity between atoms, precluding simulations that involve reactive events. The ReaxFF method was developed to help bridge this gap. Approaching the gap from the classical side, ReaxFF casts the empirical interatomic potential within a bond-order formalism, thus implicitly describing chemical bonding without expensive QM calculations. This article provides an overview of the development, application, and future directions of the ReaxFF method

Jet quenching in shock waves

We study the propagation of an ultrarelativistic light quark jet inside a shock wave using the holographic principle. The maximum stopping distance and its dependency on the energy of the jet is obtained

Odderon and seven Pomerons: QCD Reggeon field theory from JIMWLK evolution

We reinterpret the JIMWLK/KLWMIJ evolution equation as the QCD Reggeon field theory (RFT). The basic "quantum Reggeon field" in this theory is the unitary matrix $R$ which represents the single gluon scattering matrix. We discuss the peculiarities of the Hilbert space on which the RFT Hamiltonian acts. We develop a perturbative expansion in the RFT framework, and find several eigenstates of the zeroth order Hamiltonian. The zeroth order of this perturbation preserves the number of $s$ - channel gluons. The eigenstates have a natural interpretation in terms of the $t$ - channel exchanges. Studying the single $s$ - channel gluon sector we find the eigenstates which include the reggeized gluon and five other colored Reggeons. In the two ($s$ - channel) gluon sector we study only singlet color exchanges. We find five charge conjugation even states. The bound state of two reggeized gluons is the standard BFKL Pomeron. The intercepts of the other Pomerons in the large $N$ limit are $1+\omega_P=1+2\omega$ where $1+\omega$ is the intercept of the BFKL Pomeron, but their coupling in perturbation theory is suppressed by at least $1/N^2$ relative to the double BFKL Pomeron exchange. For the $[27,27]$ Pomeron we find $\omega_{[27,27]}=2\omega+O(1/N)>2\omega$. We also find three charge conjugation odd exchanges, one of which is the unit intercept Bartels-Lipatov-Vacca Odderon, while another one has an interecept greater than unity. We explain in what sense our calculation goes beyond the standard BFKL/BKP calculation. We make additional comments and discuss open questions in our approach.Comment: 58 pages, 4 figures, Extended version. To appear in JHE

Social perception in synaesthesia for colour

Synaesthesia is a rare phenomenon in which stimulation in one modality (e.g. audition) evokes a secondary percept not associated with the first (e.g. colour). Although there is a significant body of research investigating the mechanisms underlying synaesthetic experiences, it is only recently that studies have begun to investigate broader traits associated with the condition. Prior work has suggested links between synaesthesia and other neurodevelopmental conditions that are linked to altered social perception abilities. With this in mind, here we sought to examine social perception abilities in grapheme-colour synaesthesia (where achromatic graphemes evoke colour experiences) by examining facial identity and facial emotion perception in grapheme-colour synaesthetes and non-synaesthete controls. Our results indicate that individuals who experience grapheme-colour synaesthesia outperformed controls on tasks involving fine visual discrimination of facial identity and emotion, but not on tasks involving holistic face processing. These findings are discussed in the context of broader perceptual and cognitive traits previously associated with synaesthesia for colour, with the suggestion that performance benefits shown by grapheme-colour synaesthetes on fine visual discrimination of facial identity and emotion may be related to domain-general visual discrimination biases observed in this group

Anti-HTLV antibody profiling reveals an antibody signature for HTLV-I-Associated Myelopathy/Tropical Spastic Paraparesis (HAM/TSP)

<p>Abstract</p> <p>Background</p> <p>HTLV-I is the causal agent of adult T cell leukemia (ATLL) and HTLV-I-associated myelopathy/tropical spastic paraparesis (HAM/TSP). Biomarkers are needed to diagnose and/or predict patients who are at risk for HAM/TSP or ATLL. Therefore, we investigated using luciferase immunoprecipitation technology (LIPS) antibody responses to seven HTLV-I proteins in non-infected controls, asymptomatic HTLV-I-carriers, ATLL and HAM/TSP sera samples. Antibody profiles were correlated with viral load and examined in longitudinal samples.</p> <p>Results</p> <p>Anti-GAG antibody titers detected by LIPS differentiated HTLV-infected subjects from uninfected controls with 100% sensitivity and 100% specificity, but did not differ between HTLV-I infected subgroups. However, anti-Env antibody titers were over 4-fold higher in HAM/TSP compared to both asymptomatic HTLV-I (<it>P </it>< 0.0001) and ATLL patients (<it>P </it>< 0.0005). Anti-Env antibody titers above 100,000 LU had 75% positive predictive value and 79% negative predictive value for identifying the HAM/TSP sub-type. Anti-Tax antibody titers were also higher (<it>P </it>< 0.0005) in the HAM/TSP compared to the asymptomatic HTLV-I carriers. Proviral load correlated with anti-Env antibodies in asymptomatic carriers (<it>R </it>= 0.76), but not in HAM/TSP.</p> <p>Conclusion</p> <p>These studies indicate that anti-HTLV-I antibody responses detected by LIPS are useful for diagnosis and suggest that elevated anti-Env antibodies are a common feature found in HAM/TSP patients.</p

Janus Black Holes

In this paper Janus black holes in AdS3 are considered. These are static solutions of an Einstein-scalar system with broken translation symmetry along the horizon. These solutions are dual to interface conformal field theories at finite temperature. An approximate solution is first constructed using perturbation theory around a planar BTZ black hole. Numerical and exact solutions valid for all sets of parameters are then found and compared. Using the exact solution the thermodynamics of the system is analyzed. The entropy associated with the Janus black hole is calculated and it is found that the entropy of the black Janus is the sum of the undeformed black hole entropy and the entanglement entropy associated with the defect.Comment: 28 pages, 2 figures, reference adde