Mechanism of methanol decomposition on the Pd/WC(0001) surface unveiled by first-principles calculations

In this study, the decomposition of methanol into the CO and H species on the Pd/tungsten carbide (WC)(0001) surface is systematically investigated using periodic density functional theory (DFT) calculations. The possible reaction pathways and intermediates are determined. The results reveal that saturated molecules, i.e., methanol and formaldehyde, adsorb weakly on the Pd/ WC(0001) surface. Both CO and H prefer three-fold sites, with adsorption energies of −1.51 and −2.67 eV, respectively. On the other hand, CH₃O stably binds at three-fold and bridge sites, with an adsorption energy of −2.58 eV. However, most of the other intermediates tend to adsorb to the surface with the carbon and oxygen atoms in their sp³ and hydroxyl-like configurations, respectively. Hence, the C atom of CH₂OH preferentially attaches to the top sites, CHOH and CH₂O adsorb at the bridge sites, while COH and CHO occupy the three-fold sites. The DFT calculations indicate that the rupture of the initial C–H bond promotes the decomposition of CH₃OH and CH₂OH, whereas in the case of CHOH, O–H bond scission is favored over the C–H bond rupture. Thus, the most probable methanol decomposition pathway on the Pd/WC(0001) surface is CH₃OH → CH₂OH → trans-CHOH → CHO → CO. The present study demonstrates that the synergistic effect of WC (as carrier) and Pd (as catalyst) alters the CH₃OH decomposition pathway and reduces the noble metal utilization.     

双排桩门架—锚杆新型组合支护体系的应用研究

本文分析了双排桩门架支护结构的受力机理。针对工程实际进行变形分析,提出增设锚杆形成锚杆———双排桩门架式组合支护体系的方法,并与监测数据对比、验证。     

毗邻铁路大动脉排架式厂房拆除爆破

文章介绍了运煤车间爆破拆除工程的设计、施工经过及防后座的措施，对于复杂爆破环境的建筑物拆除有一定参考意义。     

The Cooperative Molecular Field Effect

Two‐dimensional arrangements of molecules can show remarkable cooperative electronic effects. Such effects can serve to achieve direct electronic sensing of chemical and physical processes via electrostatic effects, i.e., without transfer of charge or matter between the locus of sensing and that of detection.     

Preparation of one-dimensional polymer films by modification of a hydroxymethylbenzene self-assembled monolayer on iron with alkyltriethoxysilanes for preventing iron corrosion

A self-assembled monolayer (SAM) of p-hydroxymethylbenzene HOCH₂C₆H₄ - (HOMB) moiety adsorbed on iron by the formation of a covalent bond between carbon and iron atoms was prepared by electrochemical derivatization of an iron electrode with p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH₂C₆H₄N₂BF₄. The electrode covered with the HOMB SAM was modified with alkyltriethoxysilanes C_nH_2n+1Si(OC₂H₅)₃ (C_nTES, n = 8 or 18) to prepare a film of one-dimensional polymer. The protective ability of the polymer film was determined by polarization measurement of the covered electrode in an aerated 0.5 M NaCl solution. The ability was enhanced by modification of the HOMB SAM with C_nTES markedly. The iron surface coated with the one-dimensional polymer film of the HOMB SAM modified with C₈TES was characterized by contact angle measurement and FTIR reflection and X-ray photoelectron spectroscopies. The persistence in the protective ability of the polymer film against iron corrosion in 0.5 M NaCl may be associated with the strong adsorption via the covalent bond, revealed by electron-probe microanalysis.     

Deep‐UV Photochemistry and Patterning of (Aminoethylaminomethyl)phenethylsiloxane Self‐Assembled Monolayers

The 193 nm photochemistry of (aminoethylaminomethyl)phenethylsiloxane (PEDA) self‐assembled monolayers (SAMs) under ambient conditions is described. The primary photodegradation pathways at low exposure doses (< 100 mJ cm^–2) are benzylic C–N bond cleavage (ca. 68 %), with oxidation of the benzyl C to the aldehyde, and Si–C bond cleavage (ca. 32 %). Amine‐containing photoproducts released from the SAM during exposure remain physisorbed on the surface, where they undergo secondary photolysis leading to their complete degradation and removal after ca. 1200 mJ cm^–2. NaCl(aq) post‐exposure rinsing removes the physisorbed materials, showing that degradation of the original PEDA species (leaving Si–OH) is substantially complete after ca. 450 mJ cm^–2. Consequently, patterned, rinsed PEDA SAMs function as efficient templates for fabrication of high‐resolution, negative‐tone, electroless metal and DNA features with good selectivity at low dose (i.e., ca. 400 mJ cm^–2) via materials grafting to the intact amines remaining in the unirradiated PEDA SAM regions.     

Optical and structural properties of MOVPE grown GaxIn1−xAs/InP strained multiple quantum well atructures

This paper presents a study of the structural and optical properties of strained GaInAs/ InP multiple quantum well (MQW) structures fabricated by LP-MOVPE. The composition of the Ga _x In_1−x As films ranged fromx = 0.17 tox = 1.0 and was determined by sputtered neutral mass spectrometry (SNMS) on thick layers. The structures of the MQW samples with well widths from 1.5 to 5 nm were investigated by high resolution x-ray diffraction (HR-XRD). Simulations of the diffraction patterns showed that transition layers of approximately 2 monolayer (ML) thickness with high lattice mismatch exist at the interfaces. Photoluminescence (PL) measurements indicate well widths of a multiple of a monolayer with local variations of one monolayer. The PL peak energies vary smoothly with the Ga concentration. These results were confirmed by optical absorption measurements.     

Vibrational Mode in Two-Dimensional Dust Monolayer with Finite Size Dust Grains

Vibrational mode in a two-dimensional dust monolayer is investigated by considering the finite size of dust grains. Each dust grain is assumed to be a negative point charge and a dipole moment due to the inhomogeneous charge distribution on its surface. The dispersion relation of the vibrational mode is derived. Both the self-excited and externally excited cases are discussed. It is shown that the mode is sensitive to the direction of the dipole moment.     

A carboxyalkanethiol monolayer modified electrode for blocking of ascorbic acid oxidation and its application to a biosensor

Upon the application of amperometric biosensor to the biological fluid, ascorbic acid interferes the amperometric determination of analytes, because the oxidative potential of ascorbic acid is lower than that of electro active substances such as H₂O₂ produced by the enzymatic reaction. In this study we propose a method to block ascorbic acid based on the electrostatic interaction with self-assembled monolayer (SAM) and its application of the surface modified electrode to biosensor. In order to form SAM on the gold electrode with carboxyl group, 7-carboxy-heptanethiol (7-CHT) was used. The 7-CHT modified electrode did not show anodic response to ascorbic acid, but oxidized phenanthroline cobalt complex [Co(phen)₃²⁺], which can be used as a mediator of biosensor. Thus, the 7CHT-modified electrode was applied to biosensor mediated with Co(phen)₃²⁺. Fructose dehydrogenase (FDH) was immobilized to the 7-CHT modified electrode. Fructose was determined selectively with the FDH/7-CHT modified electrode at the range of 0.2-2 mM.