Surface voltammetric dealloying investigation on PdCu/C electrocatalysts toward ethanol oxidation in alkaline media

Voltammetric dealloying is employed here to investigate the correlations between catalytic performance and surface composition and structure, taking ethanol oxidation reaction (EOR) on Pd-Cu alloy surface as a case study. First, home-made PdCu/C with a mean particle size of ca. 3.11?±?0.6 nm is dealloyed by repetitive potential cycling in 0.5 M H₂SO₄. With dealloying cycles rising, the Cu component is gradually leached out and the corresponding Pd/Cu atomic ratio gradually increases from ca. 2.1 to 4.0; meanwhile, SEM images display that Pd-rich porous shell is formed due to dealloying-induced surface structural rearrangement, being verified by the appearance of ear-like peaks at ??0.015 V (vs. SCE) in CVs collected in 0.5 M H₂SO₄; furthermore, XPS spectra indicate that core-level binding energies of Pd 3d_5/2 first positively shift to 336.1 eV and then oppositively move down to 334.9 eV, indicating that the d-band center of Pd composition is modulated by the dealloying treatment. Moreover, the voltammetric peak current densities for EOR follow the order of PdCu/C-DA15?>?as-prepared PdCu/C ??>?PdCu/C-DA30 ? commercial Pd/C ? PdCu/C-DA75, due to the modest downshift of Pd d-band center resulted by charge transfer and surface atomic rearrangement. In addition, the EOR durability gradually decays with the continuous loss of Cu, indicating that electro-oxidation of surface species also follows the so-called bi-functional mechanism. This work might provide some new insights into the catalysis enhancement by tuning the surface/interfacial structure of catalysts.

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Graphical abstract The voltammetric peak current densities for ethanol oxidation on home-made PdCu/C catalysts gradually decrease with the dealloying cycles rising, suggesting that the surface voltammetric dealloyment could effectively modulate the surface composition and structure, so as to tune the catalytic performance.

     

Optimization of Fabry-Perot ring resonator embedding a grating based mirror

We study a triangular arrangement of two flat mirrors and a grating mirror for coupling a \(-1{\mathrm{st}}\) diffracted order light beam into a traveling-wave intra-cavity light recirculation and out-of-cavity output, combining the \(0\,{\mathrm{th}}\) and the repeatedly diffracted secondary \(+1{\mathrm{st}}\) order beams. The thus designed and then optimized grating Fabry-Perot ring cavity demonstrates high output contrast and detection resolution for wavelength, cavity length and incidence angle.     

Discrete and selective absorption in crystalline molecular nanofilms

Recent research in nano-optical engineering and in nanomedicine as well, seeks for methods of construction of various types of nano-markers, nano-carriers, and ways to deliver drugs to the exactly determined regions of body. In this process it is important to find methods of recognition of certain types of molecules. It is obvious that optical recognition would be the easiest and the most effective way to do it. Our research presents a model of a molecular ultrathin crystalline film and generated exciton system inside it and corresponding methodology of analysis of their optical characteristics. Properties of these spatially very restricted structures are very sensitive to their surrounding surfaces. Using the two-time Green’s functions adapted for crystalline structures with symmetry breaking, and graphical-numerical software, we have calculated the energy spectra and possible exciton states. We have shown that the appearance and the presence of localized states on the surfaces and in the boundary layers of the film depend on the thickness of the film and the film surroundings, presented through the perturbation of parameters on surfaces. Optical properties in these structures demonstrate discrete and very selective resonant absorption spectra, depending on the perturbation on their surfaces.     

A cryptosystem based on deterministic phase masks and fractional Fourier transform deploying singular value decomposition

In this paper, an asymmetric cryptosystem has been proposed to enhance the security of DRPE. The traditional DRPE scheme is thus tweaked by using fractional Fourier transform (FrFT), a class of structured phase masks called as deterministic phase masks (DMKs) and deploying singular value decomposition (SVD). In specific, we propose to organise the encryption procedure by using two DMKs and FrFT, additionally deploying SVD. On the decryption front, the input image is recovered by utilising the inverse singular value decomposition (ISVD) and an angular portion of the deterministic phase masks. The use of FrFT for encryption and decryption would enhance the robustness of DRPE scheme. Deployment of SVD on our asymmetric cryptosystem provides three components for cipher image is yet another added feature that hardens the security of DRPE scheme. DMKs are formed by the deviation from conventional rectangular function and limited range values which delivers key components with reduced size, better performance and lower complexity. The capability study of defined method, includes analysis on SVD, histogram and correlation coefficient. Our system is subject to an occlusion attack and noise attack to evaluate its performance and reliability. Computational analysis outputs and security investigation are offered in aspect to determine the security potential of proposed system. Comparative results are shown for values of mean-square-error and peak-signal-to-noise ratio of DRPE schemes.     

Gold chloride cluster ions generated by vacuum laser ablation

In this work, a simple way for study the possibility of formation a vapor cluster species of tetrachloroauric acid (HAuCl₄), using the laser ablation in the absence of a buffer or reactive atmosphere, and without a postablation supersonic expansion on a commercial matrix assisted laser desorption/ionization time-of-flight mass spectrometer, is reported. Tetrachloroauric acid is known as precursor for the synthesis of gold nanostructures and the complex salts; therefore it is an important task to discover and quantify the species arising from HAuCl₄, in order to understand their role in the gold assisted reactions. Mass spectrum of HAuCl₄ in a reflector negative-ion mode contains the hydrated mono- and dinuclear gold clusters in the m/z range 286–436, and gold chloride clusters in the m/z range 447–795. In the first part of spectrum, m/z range 286–436, the hydrated gold cluster species of type Au _n ^? (H₂O)_m (n?=?1–2; m?=?1, 2, 5, 7, 8) and [Au_n(OH)_k]^?(H₂O)_m (n?=?1–2; k?=?1–2; m?=?1, 4–8) were found. Besides that, there are gold chloride clusters with general formula [AuH_r(HCl)₂]^?(H₂O)_m (m?=?1–5; 8–9; r?=?0–2) in this part of spectrum. In the second part of spectrum, the m/z range 447–795, only gold chloride clusters were obtained. Their general formulae can be written as [AuCl_t(HCl)_v]^?(H₂O)_m (t?=?1–4; v?=?5–8; m?=?2–4, 6–8) and [Au_n(HCl)_v]^?(H₂O)_m (n?=?1–2, v?=?4–5, m?=?1–2, 5, 7). The analysis of concentration effects on the LDI mass spectra of gold clusters reveals that the relative intensities of signals for the mono- and dinuclear Au clusters increase with decreasing the concentration of water HAuCl₄ solutions.     

Controlling theoretically total absorption in hybrid-cavity resonator with one graphene monolayer outside cavity

Total absorption is realized theoretically in a graphene-outside-cavity resonator. The structure is composed of the FP-Fano hybrid resonance cavity. Changing the thickness of grating exciting Fano resonance, the absorption-mode number can be tuned effectively. For the focused double-mode absorption, the resonances behave insensitively with the variation of chemical potential of graphene. Varying the geometry of grating can control the coupling extent of two modes. Also, by manipulating the period number of two-side multilayers around graphene, the absorption, shift and number of modes are governed.     

The dependence of the conduction band edge of the alkali earth metal bismuthates on their composition

We present a comparative analysis of the conduction band edge of the alkali earth metal bismuthates containing Mg, Ca, Sr, and Ba. The conduction band edges were computed using the method suggested by Butler and Ginley. The calculations reveal that they depend on the bismuthate’s composition and vary over a wide range. We demonstrate that the energy of the conduction band increases in the series Ca?→?Sr?→?Ba. It also increases with an increase of the alkali earth metal content. The performed calculations help to determine the potential alkali earth metal bismuthate photocatalysts. The most promising compositions found in this study include strontium and barium bismuthates in which the number of the alkali earth metal atoms in the cationic sublattice exceeds the number of the bismuth atoms.     

Some types of dark soliton interactions in inhomogeneous optical fibers

Dark solitons are the subject of intense theoretical and experimental studies in nonlinear optics due to their unique characteristics compared with bright solitons. In this paper, the variable coefficient high-order nonlinear Schrödinger equation in the inhomogeneous optical fiber is investigated. Via the Hirota bilinear method and symbolic computation, the analytic dark two-soliton solutions are obtained. With the suitable choices of functions and coefficients for the obtained dark two-soliton solutions, some new phenomena are presented for the first time. The influences on phases and amplitudes of soliton interactions are detailed analyzed. Moreover, sets of double-triangle structures and methods of changing the propagation direction of dark solitons are introduced. Finally, by choosing suitable functions of the fourth-order dispersion parameter, the arch-structure and M-structure interactions are revealed. Results may be potentially useful in designing all-optical switches and optical fibers.     

Supercontinuum generation with femtosecond optical pulse compression in silicon photonic crystal fibers at 2500 nm

In this paper, femtosecond optical pulses compression and supercontinuum generation in a triangular silicon photonic crystal fiber at 2500 nm are investigated. A region of large minimum anomalous group velocity dispersion, negligible higher order dispersions and unique nonlinearity of silicon are used to demonstrate compression of 100 fs initial input optical pulses to 2.5 fs and ultra-broadband supercontinuum generation with very low input pulse energy over short distances of the fiber.     

Injection-locked range and linewidth measurements at different seed-laser linewidths using a Fabry–Pérot laser-diode

In this paper we experimentally examine the dependence of the injection-locked range magnitude of a Fabry–Pérot (FP) laser on the linewidth of a seed laser. We measure the enhancement of the incident-power-dependent injection-locked range when changing the seed-light linewidth in three different ranges, starting with tens of GHz, then hundreds of MHz, and up to a few hundred kHz. We notice the progressive shrinkage of the locking range with an increase in the linewidth of the seed source. Simultaneously, the linewidth of a FP laser was measured and the cancellation of multiple longitudinal operating modes as well as a great reduction of linewidth are observed with a self-homodyne measurement.