Mechanistic Study of 1,3-Butadiene Formation in Acetylene Hydrogenation over the Pd-Based Catalysts Using Density Functional Calculations

Green oil, which leads to the deactivation of the catalysts used for the selective hydrogenation of acetylene, has long been observed but its formation mechanism is not fully understood. In this work, the formation of 1,3-butadiene, known to be the precursor of green oil, on both Pd(111) and Pd(211) surfaces is examined using density functional theory calculations. The pathways containing C-2 + C-2 coupling reactions as well as the corresponding hydrogenation reactions are studied in detail. Three pathways for 1,3-butadiene production, namely coupling plus hydrogenation and further hydrogenation, hydrogenation plus coupling plus hydrogenation, and a two step hydrogenation followed by coupling, are determined. By comparing the effective barriers, we identify the favored pathway on both surfaces. A general understanding toward the deactivation process of the industrial catalysts is also provided. In addition, the effects of the formation of subsurface carbon atoms as well as the Ag alloying on the 1,3-butadiene formation on Pd-based catalysts are also investigated and compared with experimental results.

Predominance of entanglement of formation over quantum discord under quantum channels

We present a study of the behavior of two different figures of merit for quantum correlations, entanglement of formation and quantum discord, under quantum channels showing how the former can, counterintuitively, be more resilient to such environments spoiling effects. By exploiting strict conservation relations between the two measures and imposing necessary constraints on the initial conditions we are able to explicitly show this predominance is related to build-up of the system-environment correlations.

Individual differences provide psychophysical evidence for separate on- and off-pathways deriving from short-wave cones

Distinct neural populations carry signals from short-wave (S) cones. We used individual differences to test whether two types of pathways, those that receive excitatory input (S+) and those that receive inhibitory input (S-), contribute independently to psychophysical performance. We also conducted a genome-wide association study (GWAS) to look for genetic correlates of the individual differences. Our psychophysical test was based on the Cambridge Color Test, but detection thresholds were measured separately for S-cone spatial increments and decrements. Our participants were 1060 healthy adults aged 16-40. Test-retest reliabilities for thresholds were good (ρ=0.64 for S-cone increments, 0.67 for decrements and 0.73 for the average of the two). "Regression scores," isolating variability unique to incremental or decremental sensitivity, were also reliable (ρ=0.53 for increments and ρ=0.51 for decrements). The correlation between incremental and decremental thresholds was ρ=0.65. No genetic markers reached genome-wide significance (p-7). We identified 18 "suggestive" loci (p-5). The significant test-retest reliabilities show stable individual differences in S-cone sensitivity in a normal adult population. Though a portion of the variance in sensitivity is shared between incremental and decremental sensitivity, over 26% of the variance is stable across individuals, but unique to increments or decrements, suggesting distinct neural substrates. Some of the variability in sensitivity is likely to be genetic. We note that four of the suggestive associations found in the GWAS are with genes that are involved in glucose metabolism or have been associated with diabetes.

Counterphase modulation flicker photometry: phenotypic and genotypic associations

The OSCAR test, a clinical device that uses counterphase flicker photometry, is believed to be sensitive to the relative numbers of long-wavelength and middle-wavelength cones in the retina, as well as to individual variations in the spectral positions of the photopigments. As part of a population study of individual variations in perception, we obtained OSCAR settings from 1058 participants. We report the distribution characteristics for this cohort. A randomly selected subset of participants was tested twice at an interval of at least one week: the test-retest reliability (Spearman's rho) was 0.80. In a whole-genome association analysis we found a provisional association with a single nucleotide polymorphism (rs16844995). This marker is close to the gene RXRG, which encodes a nuclear receptor, retinoid X receptor γ. This nuclear receptor is already known to have a role in the differentiation of cones during the development of the eye, and we suggest that polymorphisms in or close to RXRG influence the relative probability with which long-wave and middle-wave opsin genes are expressed in human cones.

Performance enhancement of a wideband spiral antenna using a stepped ground plane

This study presents the use of a stepped ground plane as a means to increase the gain and front-to-back ratio of an Archimedean spiral which operates in the frequency range 3–10 GHz. The backing structure is designed to optimize the antenna performance in discrete 1 GHz bands by placing each of the eight metal steps one quarter wavelength below the corresponding active regions of the spiral. Simulated and experimental results show that this type of ground plane can be designed to enhance the antenna performance over the entire 105% operating bandwidth of the spiral.

Selective Hydrogenation of Acetylene over Pd-Boron Catalysts: A Density Functional Theory Study

Boron-modified Pd catalysts have shown excellent performance for the selective hydrogenation of alkynes experimentally. In the current work, we investigated the hydrogenation of acetylene on boron-modified Pd(111) and Pd(211) surfaces, utilizing density functional theory calculations. The activity of acetylene hydrogenation has been studied by estimating the effective barrier of the whole process. The selectivity of ethylene formation is investigated from a comparison between the desorption and the hydrogenation of ethylene as well as comparison between the ethylene and the 1,3-butadiene formation. Formation of subsurface carbon and hydrogen on both boron-modified Pd(111) and Pd(211) surfaces has also been evaluated, since these have been reported to affect both the activity and the selectivity of acetylene hydrogenation to produce ethylene on Pd surfaces. Our results provide some important insights into the Pd B catalysts for selective hydrogenation of acetylene and also for more complex hydrogenation systems, such as stereoselective hydrogenation of longer chain alkynes and selective hydrogenation of vegetable oil.

A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu-ZSM-5

A low temperature, isothermal, gas-phase, recyclable process is described for the partial oxidation of methane to methanol over Cu–ZSM-5. Activation in NO at 150 °C followed by methane reaction and steam extraction (both at 150 °C) allowed direct observation of methanol at the reactor outlet.

Polymerisable squaramide receptors for anion binding and sensing

A novel series of polymerisable squaramides has been synthesised in high yields using simple chemical reactions, and evaluated in the binding of anionic species. These vinyl monomers can be used as functional building blocks in co-polymerisations with a plethora of co-monomers or cross-linkers, grace to their compatibility with free-radical polymerisation reactions. Aromatic substituted squaramides were found to be the strongest receptors, while binding of certain anions was accompanied by a strong colour change, attributed to the de-protonation of the squaramide. The best performing squaramide monomers were incorporated in molecularly imprinted polymers (MIPs) targeting a model anion and their capacities and selectivity were evaluated by rebinding experiments. Polymers prepared using the new squaramide monomers were compared to urea based co-polymers, and were found to contain up to 80% of the theoretical maximum number of binding sites, an exceptionally high value compared to previous reports. Strong polymer colour changes were observed upon rebinding of certain anions, equivalent to those witnessed in solution, paving the way for application of such materials in anion sensing devices.



Graphical abstract: Polymerisable squaramide receptors for anion binding and sensing

Nonreciprocal scattering by stacked nonlinear magneto-active semiconductor layers

The combinatorial frequency generation by the periodic stacks of magnetically biased semiconductor layers has been modelled in a self-consistent problem formulation, taking into account the nonlinear dynamics of carriers. It is shown that magnetic bias not only renders nonreciprocity of the three-wave mixing process but also significantly enhances the nonlinear interactions in the stacks, especially at the frequencies close to the intrinsic magneto-plasma resonances of the constituent layers. The main mechanisms and properties of the combinatorial frequency generation and emission from the stacks are illustrated by the simulation results, and the effects of the individual layer parameters and the structure arrangement on the stack nonlinear and nonreciprocal response are discussed. © 2014 Elsevier B.V. All rights reserved.

Brillouin scattering of light by spin waves in ferromagnetic nanorods

We report the investigations of spin wave modes of arrays of Ni and Co nanorods using Brillouin light scattering. We have revealed the significant influence of spin wave modes along the nanorod axis in contrast to infinite magnetic nanowires. Unusual optical properties featuring an inverted Stokes/anti-Stokes asymmetry of the Brillouin scattering spectra have been observed. The spectrum of spin wave modes in the nanorod array has been calculated and compared with the experiment. Experimental observations are explained in terms of a combined numerical-analytical approach taking into account both the low aspect ratio of individual magnetic nanorods and dipolar magnetic coupling between the nanorods in the array. The optical studies of spin-wave modes in nanorod metamaterials with low aspect ratio nanorods have revealed new magnetic and magneto-optical properties compared to continuous magnetic films or infinite magnetic nanowires. Such magnetic artificial materials are important class of active metamaterials needed for prospective data storage and signal processing applications. © 2012 Elsevier B.V.

Dipolar emission in trench metal-insulator-metal waveguides for short-scale plasmonic communications: numerical optimization

Here we consider the numerical optimization of active surface plasmon polariton (SPP) trench waveguides suited for integration with luminescent polymers for use as highly localized SPP source devices in short-scale communication integrated circuits. The numerical analysis of the SPP modes within trench waveguide systems provides detailed information on the mode field components, effective indices, propagation lengths and mode areas. Such trench waveguide systems offer extremely high confinement with propagation on length scales appropriate to local interconnects, along with high efficiency coupling of dipolar emitters to waveguided plasmonic modes which can be close to 80%. The large Purcell factor exhibited in these structures will further lead to faster modulation capabilities along with an increased quantum yield beneficial for the proposed plasmon-emitting diode, a plasmonic analog of the light-emitting diode. The confinement of studied guided modes is on the order of 50 nm and the delay over the shorter 5 μm length scales will be on the order of 0.1 ps for the slowest propagating modes of the system, and significantly less for the faster modes.

High-impedance metasurfaces with interwoven conductor patterns

High impedance metasurfaces (HIMSs) formed by interwoven conductor arrays are proposed. Bandwidth comparable with that of the basic square patches is achieved at an order of magnitude smaller unit cells. The presented structures are apt for small mobile terminals and low frequency applications.

Interwoven spiral arrays on ferrite-dielectric substrates for high-impedance metasurfaces

A high impedance metasurface (HIMS) composed of the arrays of intertwined planar spirals on thin (~0.1λ) ferrite-dielectric substrate is proposed. The HIMS exhibits fractional bandwidth in excess of 10% and excellent angular and polarisation stability of the circular polarised waves at oblique incidence.

Macroscopicity in an optomechanical matter-wave interferometer

We analyse a proposal that we have recently put forward for an interface between matter-wave and optomechanical technologies from the perspective of macroscopic quantumness. In particular, by making use of a measure of macroscopicity in quantum superpositions that is particularly well suited for continuous variables systems, we demonstrate the existence of working points for our interface at which a quantum mechanical superposition of genuinely mesoscopic states is achieved. Our proposal thus holds the potential to affirm itself as a viable atom-to-mechanics transducer of quantum coherences.

Identifying PV module mismatch faults by a thermography-based temperature distribution analysis

Photovoltaic (PV) solar power generation is proven to be effective and sustainable but is currently hampered by relatively high costs and low conversion efficiency. This paper addresses both issues by presenting a low-cost and efficient temperature distribution analysis for identifying PV module mismatch faults by thermography. Mismatch faults reduce the power output and cause potential damage to PV cells. This paper first defines three fault categories in terms of fault levels, which lead to different terminal characteristics of the PV modules. The investigation of three faults is also conducted analytically and experimentally, and maintenance suggestions are also provided for different fault types. The proposed methodology is developed to combine the electrical and thermal characteristics of PV cells subjected to different fault mechanisms through simulation and experimental tests. Furthermore, the fault diagnosis method can be incorporated into the maximum power point tracking schemes to shift the operating point of the PV string. The developed technology has improved over the existing ones in locating the faulty cell by a thermal camera, providing a remedial measure, and maximizing the power output under faulty conditions.