Factors influencing the catalytic oxidation of benzyl alcohol using supported phosphine-capped gold nanoparticles

Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.Two phosphine-stabilised gold clusters, Au101(PPh3)21Cl5 and Au9(PPh3)8(NO3)3, were deposited and activated on anatase TiO2 and fumed SiO2. These catalysts showed an almost complete oxidation of benzyl alcohol (>90%) within 3 hours at 80 °C and 3 bar O2 in methanol with a high substrate-to-metal molar ratio of 5800 and turn-over frequency of 0.65 s−1. Factors influencing catalytic activity were investigated, including metal–support interaction, effects of heat treatments, chemical composition of gold clusters, the size of gold nanoparticles and catalytic conditions. It was found that the anions present in gold clusters play a role in determining the catalytic activity in this reaction, with NO3− diminishing the catalytic activity. High catalytic activity was attributed to the formation of large gold nanoparticles (>2 nm) that coincides with partial removal of ligands which occurs during heat treatment and catalysis. Selectivity towards the formation of methyl benzoate can be tuned by selection of the reaction temperature. The catalysts were characterised using transmission electron microscopy, UV-vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy

Exact Study of the Effect of Level Statistics in Ultrasmall Superconducting Grains

The reduced BCS model that is commonly used for ultrasmall superconducting grains has an exact solution worked out long ago by Richardson in the context of nuclear physics. We use it to check the quality of previous treatments of this model, and to investigate the effect of level statistics on pairing correlations. We find that the ground state energies are on average somewhat lower for systems with non-uniform than uniform level spacings, but both have an equally smooth crossover from the bulk to the few-electron regime. In the latter, statistical fluctuations in ground state energies strongly depend on the grain's electron number parity.Comment: 4 pages, 3 eps figs, RevTe

Guided Inquiry Learning in an Introductory Chemistry Course

Foundations of Chemistry (FoC), the University of Adelaide’s introductory chemistry pathway, recently underwent a complete restructure to assume no prior chemistry knowledge in order to better cater to students with little or no chemistry background. The restructure introduced Process-Oriented Guided Inquiry Learning (POGIL) style activities in lectures to deliver the majority of the course content and a new online learning platform for summative assessment. Three entirely new FoC courses were developed, one in each of semester 1 (FoC IA), semester 2 (FoC IB) and the University’s Summer Semester (FoC IS). Successful completion of all three courses provides students with a pathway into second year Chemistry in addition to the pathway provided by completing Chemistry IA and IB. To date, FoC IS has run from 2013 to 2015, with half of the students in each of these classes progressing to level II Chemistry courses. This paper outlines the restructure process that led to the creation of three new courses and how these developments have impacted student learning outcomes. Students have responded positively to the restructured courses, and end-of-semester results for FoC IA and IB have seen an increase in the proportion of Distinction and High Distinction grades

Diagonal-unitary 2-designs and their implementations by quantum circuits

We study efficient generations of random diagonal-unitary matrices, an ensemble of unitary matrices diagonal in a given basis with randomly distributed phases for their eigenvalues. Despite the simple algebraic structure, they cannot be achieved by quantum circuits composed of a few-qubit diagonal gates. We introduce diagonal-unitary $t$-designs and present two quantum circuits that implement diagonal-unitary $2$-designs with the computational basis in $N$-qubit systems. One is composed of single-qubit diagonal gates and controlled-phase gates with randomized phases, which achieves an exact diagonal-unitary $2$-design after applying the gates on all pairs of qubits. The number of required gates is $N(N-1)/2$. If the controlled-Z gates are used instead of the controlled-phase gates, the circuit cannot achieve an exact $2$-design, but achieves an $\epsilon$-approximate $2$-design by applying gates on randomly selected pairs of qubits. Due to the random choice of pairs, the circuit obtains extra randomness and the required number of gates is at most $O(N^2(N+\log1/\epsilon))$. We also provide an application of the circuits, a protocol of generating an exact $2$-design of random states by combining the circuits with a simple classical procedure requiring $O(N)$ random classical bits.Comment: Revised, 22 pages + Appendix, 3 figures; major revision from v2; presentation is improved in v4; v5 is a published versio

Statistical Properties of Cross-Correlation in the Korean Stock Market

We investigate the statistical properties of the correlation matrix between individual stocks traded in the Korean stock market using the random matrix theory (RMT) and observe how these affect the portfolio weights in the Markowitz portfolio theory. We find that the distribution of the correlation matrix is positively skewed and changes over time. We find that the eigenvalue distribution of original correlation matrix deviates from the eigenvalues predicted by the RMT, and the largest eigenvalue is 52 times larger than the maximum value among the eigenvalues predicted by the RMT. The $\beta_{473}$ coefficient, which reflect the largest eigenvalue property, is 0.8, while one of the eigenvalues in the RMT is approximately zero. Notably, we show that the entropy function $E(\sigma)$ with the portfolio risk $\sigma$ for the original and filtered correlation matrices are consistent with a power-law function, $E(\sigma) \sim \sigma^{-\gamma}$, with the exponent $\gamma \sim 2.92$ and those for Asian currency crisis decreases significantly

Evolution of wave packets in quasi-1D and 1D random media: diffusion versus localization

We study numerically the evolution of wavepackets in quasi one-dimensional random systems described by a tight-binding Hamiltonian with long-range random interactions. Results are presented for the scaling properties of the width of packets in three time regimes: ballistic, diffusive and localized. Particular attention is given to the fluctuations of packet widths in both the diffusive and localized regime. Scaling properties of the steady-state distribution are also analyzed and compared with theoretical expression borrowed from one-dimensional Anderson theory. Analogies and differences with the kicked rotator model and the one-dimensional localization are discussed.Comment: 32 pages, LaTex, 11 PostScript figure

Dynamical TAP approach to mean field glassy systems

The Thouless, Anderson, Palmer (TAP) approach to thermodynamics of mean field spin-glasses is generalised to dynamics. A method to compute the dynamical TAP equations is developed and applied to the p-spin spherical model. In this context we show to what extent the dynamics can be represented as an evolution in the free energy landscape. In particular the relationship between the long-time dynamics and the local properties of the free energy landscape shows up explicitly within this approach. Conversely, by an instantaneous normal modes analysis we show that the local properties of the energy landscape seen by the system during its dynamical evolution do not change qualitatively at the dynamical transition.Comment: final version, 21 pages, 1 eps figur

Vibrational spectrum of topologically disordered systems

The topological nature of the disorder of glasses and supercooled liquids strongly affects their high-frequency dynamics. In order to understand its main features, we analytically studied a simple topologically disordered model, where the particles oscillate around randomly distributed centers, interacting through a generic pair potential. We present results of a resummation of the perturbative expansion in the inverse particle density for the dynamic structure factor and density of states. This gives accurate results for the range of densities found in real systems.Comment: Completely rewritten version, accepted in Physical Review Letter

Off-diagonal correlations in one-dimensional anyonic models: A replica approach

We propose a generalization of the replica trick that allows to calculate the large distance asymptotic of off-diagonal correlation functions in anyonic models with a proper factorizable ground-state wave-function. We apply this new method to the exact determination of all the harmonic terms of the correlations of a gas of impenetrable anyons and to the Calogero Sutherland model. Our findings are checked against available analytic and numerical results.Comment: 19 pages, 5 figures, typos correcte

Toward control of gold cluster aggregation on TiO(2) via surface treatments

Published: October 1, 2015Well-defined Au–TiO₂ materials were synthesized by deposition of triphenylphosphine-protected Au₉ clusters on TiO₂ (Aeroxide P-25), pre-treated in eight different ways and subsequently exposed to two post-treatments. X-ray photoelectron spectroscopy and UV–vis diffuse reflectance spectroscopy studies showed that in most cases the PPh₃ ligand shell was removed upon deposition even before post-treatment, coinciding with some cluster aggregation. However, clusters deposited on TiO₂ treated using H₂SO₄ and H2O₂ showed remarkable resistance to aggregation, even after high-temperature calcination, while clusters on H₂-treated TiO₂ showed the greatest resistance to aggregation under ozonolysis.Jan-Yves Ruzicka, Faridah Abu Bakar, Christoffer Hoeck, Rohul Adnan, Campbell McNicoll, Tim Kemmitt, Bruce C. Cowie, Gregory F. Metha, Gunther G. Andersson, and Vladimir B. Golovk