A CO Adsorption Site Change Induced by Copper Substitution in a Ruthenium Catalyst for Enhanced CO Oxidation Activity

Ru is an important catalyst in many types of reactions. Specifically, Ru is well known as the best monometallic catalyst for oxidation of carbon monoxide (CO) and has been practically used in residential fuel cell systems. However, Ru is a minor metal, and the supply risk often causes violent fluctuations in the price of Ru. Performance‐improved and cost‐reduced solid‐solution alloy nanoparticles of the Cu‐Ru system for CO oxidation are now presented. Over the whole composition range, all of the Cu_xRu_1?x nanoparticles exhibit significantly enhanced CO oxidation activities, even at 70 at % of inexpensive Cu, compared to Ru nanoparticles. Only 5 at % replacement of Ru with Cu provided much better CO oxidation activity, and the maximum activity was achieved by 20 at % replacement of Ru by Cu. The origin of the high catalytic performance was found as CO site change by Cu substitution, which was investigated using in situ Fourier transform infrared spectra and theoretical calculations.     

Preparation of polymethyl methacrylate with well-controlled stereoregularity by anionic polymerization in an ionic liquid solvent

This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using ¹H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA.     

High‐performance liquid chromatography separation of unsaturated organic compounds by a monolithic silica column embedded with silver nanoparticles

The optimization of a porous structure to ensure good separation performances is always a significant issue in high‐performance liquid chromatography column design. Recently we reported the homogeneous embedment of Ag nanoparticles in periodic mesoporous silica monolith and the application of such Ag nanoparticles embedded silica monolith for the high‐performance liquid chromatography separation of polyaromatic hydrocarbons. However, the separation performance remains to be improved and the retention mechanism as compared with the Ag ion high‐performance liquid chromatography technique still needs to be clarified. In this research, Ag nanoparticles were introduced into a macro/mesoporous silica monolith with optimized pore parameters for high‐performance liquid chromatography separations. Baseline separation of benzene, naphthalene, anthracene, and pyrene was achieved with the theoretical plate number for analyte naphthalene as 36 000 m^?1. Its separation function was further extended to cis/trans isomers of aromatic compounds where cis/trans stilbenes were chosen as a benchmark. Good separation of cis/trans‐stilbene with separation factor as 7 and theoretical plate number as 76 000 m^?1 for cis‐stilbene was obtained. The trans isomer, however, is retained more strongly, which contradicts the long‐ established retention rule of Ag ion chromatography. Such behavior of Ag nanoparticles embedded in a silica column can be attributed to the differences in the molecular geometric configuration of cis/trans stilbenes.     

Estimates of eigenvalues of the Laplacian by a reduced number of subsets

Chung–Grigor’yan–Yau’s inequality describes upper bounds of eigenvalues of the Laplacian in terms of subsets (“input”) and their volumes. In this paper we will show that we can reduce “input” in Chung–Grigor’yan–Yau’s inequality in the setting of Alexandrov spaces satisfying CD(0,∞). We will also discuss a related conjecture for some universal inequality among eigenvalues of the Laplacian.     

Further properties of the forward–backward envelope with applications to difference-of-convex programming

In this paper, we further study the forward–backward envelope first introduced in Patrinos and Bemporad (Proceedings of the IEEE Conference on Decision and Control, pp 2358–2363, 2013) and Stella et al. (Comput Optim Appl, doi: 10.1007/s10589-017-9912-y, 2017) for problems whose objective is the sum of a proper closed convex function and a twice continuously differentiable possibly nonconvex function with Lipschitz continuous gradient. We derive sufficient conditions on the original problem for the corresponding forward–backward envelope to be a level-bounded and Kurdyka–?ojasiewicz function with an exponent of \(\frac{1}{2}\); these results are important for the efficient minimization of the forward–backward envelope by classical optimization algorithms. In addition, we demonstrate how to minimize some difference-of-convex regularized least squares problems by minimizing a suitably constructed forward–backward envelope. Our preliminary numerical results on randomly generated instances of large-scale \(\ell _{1-2}\) regularized least squares problems (Yin et al. in SIAM J Sci Comput 37:A536–A563, 2015) illustrate that an implementation of this approach with a limited-memory BFGS scheme usually outperforms standard first-order methods such as the nonmonotone proximal gradient method in Wright et al. (IEEE Trans Signal Process 57:2479–2493, 2009).     

Recent progress in applications of graphene oxide for gas sensing: A review

This paper is a review of the recent progress on gas sensors using graphene oxide (GO). GO is not a new material but its unique features have recently been of interest for gas sensing applications, and not just as an intermediate for reduced graphene oxide (RGO). Graphene and RGO have been well known gas-sensing materials, but GO is also an attractive sensing material that has been well studied these last few years. The functional groups on GO nanosheets play important roles in adsorbing gas molecules, and the electric or optical properties of GO materials change with exposure to certain gases. Addition of metal nanoparticles and metal oxide nanocomposites is an effective way to make GO materials selective and sensitive to analyte gases. In this paper, several applications of GO based sensors are summarized for detection of water vapor, NO₂, H₂, NH₃, H₂S, and organic vapors. Also binding energies of gas molecules onto graphene and the oxygenous functional groups are summarized, and problems and possible solutions are discussed for the GO-based gas sensors.     

Coronenetetraimide‐Centered Cruciform Pentamers Containing Multiporphyrin Units: Synthesis and Sequential Photoinduced Energy‐ and Electron‐Transfer Dynamics

A series of coronenetetraimide (CorTIm)‐centered cruciform pentamers containing multiporphyrin units, in which four porphyrin units are covalently linked to a CorTIm core through benzyl linkages, were designed and synthesized to investigate their structural, spectroscopic, and electrochemical properties as well as photoinduced electron‐ and energy‐transfer dynamics. These systems afforded the first synthetic case of coroneneimide derivatives covalently linked with dye molecules. The steady‐state absorption and electrochemical results indicate that a CorTIm and four porphyrin units were successfully characterized by the corresponding reference monomers. In contrast, the steady‐state fluorescence measurements demonstrated that strong fluorescence quenching relative to the corresponding monomer units was observed in these pentamers. Nanosecond laser flash photolysis measurements revealed the occurrence of intermolecular electron transfer from triplet excited state of zinc porphyrins to CorTIm. Femtosecond laser‐induced transient absorption measurements for excitation of the CorTIm unit clearly demonstrate the sequential photoinduced energy and electron transfer between CorTIm and porphyrins, that is, occurrence of the initial energy transfer from CorTIm (energy donor) to porphyrins (energy acceptor) and subsequent electron transfer from porphyrins (electron donor) to CorTIm (electron acceptor) in these pentamers, whereas only the electron‐transfer process from porphyrins to CorTIm was observed when we mainly excite porphyrin units. Finally, construction of high‐order supramolecular patterning of these pentamers was performed by utilizing self‐assembly and physical dewetting during the evaporation of solvent.