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.

     

Experimental analysis of spectral characteristics of antiresonant guiding photonic crystal fibers

Both numerical and experimental analyses are carried out to investigate the spectral characteristics of antiresonant guiding photonic crystal fibers. The transmission minima were observed at the wavelengths where LP(ml) (m相似文献   

Base‐dependent selectivity of an SNAr reaction

A detailed kinetic analysis and computational study of an S_NAr reaction between 2,5,6‐trifluoronicotinonitrile, 2 , and the ambident 3‐isopropoxy‐1H‐pyrazol‐5‐amine, 3 , is presented. The selectivity with respect to the reaction at the primary amino group of 2 , to give the desired product, 2,5‐difluoro‐6‐[(3‐isopropoxy‐1H‐pyrazol‐5‐yl)amino]nicotinonitrile, 1 , is strongly dependent upon reaction conditions. Reaction is found to proceed via both uncatalysed and base catalysed routes, and selectivity towards 1 is strongly enhanced in the presence of the base diazabicyclo[2,2,2]octane (DABCO). Computational studies in tetrahydrofuran solution at the B3LYP/6‐31G* level of theory have provided valuable insight into alternative kinetically indistinguishable reaction pathways. The results suggest that for reaction at the primary amino group, proton removal by DABCO accompanying amine addition allows avoidance of a high‐energy, zwitterionic Meisenheimer intermediate. Reactions at the alternative pyrazole nitrogen atoms are less sensitive to the presence of base because of stabilisation of the Meisenheimer zwitterions by intramolecular hydrogen bonding. Copyright © 2010 John Wiley & Sons, Ltd.     

Air stability of PTCDI‐C13‐based n‐OFETs on polymer interfacial layers

This Letter reports the novel use of poly(9‐vinylcarbazole) (PVK) as a dielectric interfacial layer for n‐type organic field‐effect transistors (n‐OFETs). With PVK, both the air stability and electron mobility of N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C13)‐based OFETs were improved. Among the PVKs with different weight‐average molecular weight (M_w), PVK with high M_w showed good performance. The high glass transition temperature of PVK enabled thermal post annealing of the active layer, which resulted in a high electron mobility of 0.61 cm²/Vs. This mobility was maintained at 90% and 59% after 4 days and 105 days in air, respectively. The PVK interfacial layer reduced the trapped charges in the PTCDI‐C13‐based n‐OFET for air‐exposure and caused a decrease in the threshold voltage shift.

     

Pulsed-laser photolysis of chromium and molybdenum hexacarbonyls at 308 nm: Simultaneous monitoring of optical and acoustic emissions

An acoustic technique developed earlier was applied to measure the molar number of fragments produced in the XeCl-laser-induced gas-phase photolysis of Cr(CO)₆ and Mo(CO)₆. The bluish-green Cr and Mo emissions were also monitored and correlated with the acoustic signal. For laser fluence ranging up to about 25 mJ/cm² (38 mJ/cm²), the Cr (Mo) optical signal varied with laser fluence asy =dx ³, in agreement with the model that highly excited metal atoms were produced by direct three-photon processes. The acoustic signal varied with fluence asy = ax + bx ², consistent with the model that most fragments were formed via sequential and direct two-photon processes. Quite expectedly, all coefficientsa,b andd vary linearly with carbonyl partial pressure. Both optical and acoustic signals showed onset of saturation at 25 mJ/cm² (38 mJ/cm²) for the case of chromium (molybdenum) hexacarbonyl, suggesting that all photolysis channels were equally affected by the depletion of parent molecules. By assuming a common depletion mechanism, upper limits on the branching ratios of the various photolysis channels were estimated.