Theoretical Modelling and Facile Synthesis of a Highly Active Boron‐Doped Palladium Catalyst for the Oxygen Reduction Reaction

A highly active alternative to Pt electrocatalysts for the oxygen reduction reaction (ORR), which is the cathode‐electrode reaction of fuel cells, is sought for higher fuel‐cell performance. Our theoretical modelling reveals that B‐doped Pd (Pd‐B) weakens the absorption of ORR intermediates with nearly optimal binding energy by lowering the barrier associated with O₂ dissociation, suggesting Pd‐B should be highly active for ORR. In fact, Pd‐B, facile synthesized by an electroless deposition process, exhibits 2.2 times and 8.8 times higher specific activity and 14 times and 35 times less costly than commercial pure Pd and Pt catalysts, respectively. Another computational result is that the surface core level of Pd is negatively shifted by B doping, as confirmed by XPS, and implies that filling the density of states related to the anti‐bonding of oxygen to Pd surfaces with excess electrons from B doping, weakens the O bonding to Pd and boosts the catalytic activity.     

Remarkable synergistic effect in cobalt-iron nitride/alloy nanosheets for robust electrochemical water splitting

Design and synthesis of noble-metal-free bifunctional catalysts for efficient and robust electrochemical water splitting are of significant importance in developing clean and renewable energy sources for sustainable energy consumption.Herein,a simple three-step strategy is reported to construct cobalt-iron nitride/alloy nanosheets on nickel foam(CoFe-NA/NF)as a bifunctional catalyst for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).The electrocatalyst with optimized composition(CoFe-NA2/NF)can achieve ultralow overpotentials of 73 mV and 250 mV for HER and OER,respectively,at a current density of 10 mA cm^-2 in 1 M KOH.Notably,the electrolyzer based on this electrocatalyst is able to boost the overall water splitting with a cell voltage of 1.564 V to deliver 10 mA cm^-2 for at least 50 h without obvious performance decay.Furthermore,our experiment and theoretical calculation demonstrate that the combination of cobalt-iron nitride and alloy can have low hydrogen adsorption energy and facilitate water dissociation during HER.In addition,the surface reconstruction introduces metal oxyhydroxides to optimize the OER process.Our work may pave a new pathway to design bifunctional catalysts for overall water splitting.     

Synthesis of sterically encumbered porphyrins as catalysts for shape‐selective oxidations

A general method is described for the synthesis of sterically encumbered porphyrins whose shielding superstructure can take on the enzymatic role of substrate discrimination. This method is based on an improved synthesis of pyrroles substituted with a 2,6‐dibromophenyl group, followed by a Suzuki cross‐coupling to replace the Br with aryl groups. Porphyrins assembled from such pyrrole units have a barrel shape with the metal center completely fenced by four β‐substituted terphenyl shielding wings. The Fe and Mn porphyrins prove to be excellent catalysts for regioselective epoxidation of alkenes.     

Phase equilibria in the Al-Cu-Fe system at a temperature of 853 K in the aluminum enriched region

The phase equilibria in the Al-Cu-Fe system at 853 K in the aluminum enriched region are studied using the methods of scanning and transmission electron microscopy, X-ray phase analysis, and electron probe microanalysis. An isothermal cross section of the system is constructed. Crystal lattice parameters of the phases based on binary and ternary compounds are determined. Approximant phases are not found to form in the quasicrystalline i-phase region.     

Differentiation of herbs linked to "Chinese herb nephropathy" from the liquid chromatographic determination of aristolochic acids

A HPLC method was developed and applied to analyze aristolochic acids (AA-I and AA-II) in Chinese medicinal herbs. The herb samples were extracted by using ultrasonication with the extraction efficiency of better than 82%. Extracts were then filtered and injected onto a C18 column eluting under a gradient program using methanol and water-containing 0.5% acetic acid. The method with the detection limits of 1.33 ng for AA-I and 7.29 ng for AA-II per injection was successfully applied for the analysis of traditional Chinese medicine (TCM) and related products and differentiation of Chinese medicinal herbs that have previously been misused and caused toxicological effects. The developed protocol provided an example that analysis of selected component markers could serve for health security and quality control of TCM consumption.     

Three‐dimensional visible‐light capsule enclosing perfect supersized darkness via antiresolution

Supersized darkness in three dimensions surrounded by all light in free space is demonstrated theoretically and experimentally in the visible regime. The object staying in the darkness is similar to staying in an empty light capsule because light just bypasses it by resorting to destructive interference. A binary‐optical system is designed and fabricated based on achieving antiresolution (AR), by which electromagnetic energy flux avoids and bends smoothly around a nearly perfect darkness region. AR remains an unexplored topic hitherto, in contrast to the super‐resolution for realizing high spatial resolution. This novel scheme replies on smearing out the point spread function and thus poses less stringent limitations upon the object's size and position since the created dark (zero‐field) area reach 8 orders of magnitude larger than λ² in cross‐sectional size. It functions very well with arbitrarily polarized beams in three dimensions, which is also frequency scalable in the whole electromagnetic spectrum.     

Monotonic Solutions of a Functional Equation Arising from Simultaneous Utility Representations

The functional equation ?(h(x)) ? ?(h(y)) + ?(y) = ?(h(x ? y) + y) was solved by Aczél, Luce and Marley on the assumption that the functions are different iable. They posed the question of its strictly monotonic continuous solutions. The problem is solved using a uniqueness theorem. The continuity assumption on the functions is removed and the equation is also solved on a restricted domain.     

On the almost automorphy of bounded solutions of differential equations with piecewise constant argument

In this paper we give sufficient spectral conditions for the almost automorphy of bounded solutions to differential equations with piecewise constant argument of the form x^′(t)=Ax([t])+f(t), t∈R, where A is a bounded linear operator in X and f is an X-valued almost automorphic function.     

Amorphous shear bands in deformed TiNi alloy

The structure and strain relief of TiNi alloy are examined following combined deformation consisting of quasi-hydro-extrusion followed by uniaxial compression. The shear nature of the amorphous bands resulting from such strain is demonstrated. A connection between the amorphous bands and the strain relief has been found. Fiz. Tverd. Tela (St. Petersburg) 39, 1237–1239 (July 1997)