On the Surface Nature of Bimetallic PdZn Particles Supported on a ZnO–CeO<Subscript>2</Subscript> Nanocomposite for the Methanol Steam Reforming Reaction

CO adsorption—as a molecular probe—was studied by transmission IR spectroscopy on pre-reduced Pd and bimetallic PdZn nanoparticles. Palladium was supported (2 wt% Pd) on pure CeO₂, ZnO and a ZnO–CeO₂ composite (atomic ratio Zn:Ce?=?1:2). The Pd 3d_5/2 binding energy shift, together with the formation of metallic zinc were consistent with the development of a PdZn alloy over the zinc-containing supports at increasing reduction temperature, as revealed by XPS. Following H₂ reduction at 623 K the bimetallic particles showed only linear CO adsorption (CO_L) at initial contact time (10 Torr CO, 298 K), giving rise to a convoluted IR band ascribed to different Pd sites, where it was assumed that the Pd–Pd distances were larger than for pure Pd crystallites, indicating the presence of a PdZn alloyed surface. However, for longer exposure time to CO and/or higher superimposed pressure, the appearance of bridge and hollow coordinated CO (CO_B and CO_H, respectively) on the Pd sites suggested the degradation of the PdZn surface alloy, most likely due to the segregation of Pd surface patches. The temperature-programmed, dynamic isobaric adsorption of CO (TPA-CO), under flowing CO(1%)/He on the catalysts pre-reduced at 623 K (that is, for similar conditions to those found in the methanol steam reforming—MSR-process) showed faster desorption of CO_L as compared to CO_B?+?CO_H species for supported Pd/CeO₂, as expected. However, the TPA-CO results on Pd/ZnO–CeO₂ were atypical: even under the superimposed, low CO partial pressure, and for a temperature range similar to those found at high methanol conversion in the MSR reaction, the PdZn bimetallic surface nature was recovered, which could be an explanation of the good selectivity to CO₂ of Pd/ZnO-based catalysts and—in particular—of the catalytically stable Pd/ZnO–CeO₂ materials.

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Flow influenced electrochemical corrosion of nickel aluminium bronze – Part I. Cathodic polarisation

The cathodic polarisation behaviour of CA 104 nickel aluminium bronze (NAB) has been examined in fully characterised seawaters (filtered and artificial) using the rotating disc electrode (RDE) and the rotating cylinder electrode (RCE). Linear sweep voltammetry and a potential step, current transient technique were used to examine the charge transfer and mass transfer controlled cathodic response as a function of both laminar and turbulent fluid flow. For freshly polished surfaces, the rate of irreversible charge transfer controlled oxygen reduction is controlled by the exchange of a single electron and hydrogen evolution is only significant at potentials more negative than approximately –1.0 V vs. the saturated calomel electrode (SCE).     

Modeling of Precipitation Phase Boundaries in Mixed Surfactant Systems Using an Improved Counterion Binding Model

Anionic surfactants, commonly used in household products and the detergency industry, tend to precipitate with divalent counterions in hard water. The unsightly soap scum thus formed also removes the surfactant from the cleaning action. The current research has improved prediction of the precipitation phase boundary for mixtures of surfactants in hard water in two ways: firstly, an accurate value of the solubility product (K _SP ) has been determined for the calcium salt of 4-octylbenzene sulfonate, and accurate temperature dependent K _SP values have been determined for the calcium salts of dodecyl sulfate and decyl sulfate; secondly, improvements in prediction of the precipitation phase boundary have been achieved using an improved model. The K _SP values of the decyl sulfate and dodecyl sulfate salts strongly increase with increasing temperature, with the shorter chain surfactant having significantly higher K _SP than its longer chain analogue. At 30?°C the K _SP of the 4-octylbenzenesulfonate salt is similar to that of the dodecyl sulfate salt, perhaps due to the similarity in the length of their hydrocarbon tails. A recent counterion binding model proposed by our research group and micellization models have been used to model the precipitation phase boundaries for both single anionic surfactant and binary mixed anionic surfactant systems, improving thermodynamic modeling of the precipitation phase boundary of single and binary mixed anionic surfactant systems. In particular, the improved model of counterion binding has allowed the model to predict the phase boundary accurately over a range of temperatures.     

Group sequential crossover trial designs with strong control of the familywise error rate

Crossover designs are an extremely useful tool to investigators, and group sequential methods have proven highly proficient at improving the efficiency of parallel group trials. Yet, group sequential methods and crossover designs have rarely been paired together. One possible explanation for this could be the absence of a formal proof of how to strongly control the familywise error rate in the case when multiple comparisons will be made. Here, we provide this proof, valid for any number of initial experimental treatments and any number of stages, when results are analyzed using a linear mixed model. We then establish formulae for the expected sample size and expected number of observations of such a trial, given any choice of stopping boundaries. Finally, utilizing the four-treatment, four-period TOMADO trial as an example, we demonstrate that group sequential methods in this setting could have reduced the trials expected number of observations under the global null hypothesis by over 33%.     

Comparative study of surface properties of Mg-substituted hydroxyapatite bioceramic microspheres

Mg-substituted hydroxyapatite (HAp) bioceramic microspheres were prepared by spray drying and subsequent processing at 1173, 1273 and 1373 K. Influence of various Mg substitution levels (up to 0.84 ± 0.10 wt%) on physicochemical properties of the HAp bioceramic microspheres was evaluated. Obtained results were used for the elucidation of the compositional and structural characteristics of the microspheres in conjunction with adsorption of protein, namely, bovine serum albumin (BSA). The primary difference among the microspheres processed at various temperature was the presence or absence of the micropores (<2 nm in diameter) and mesopores (between 2 and 50 nm). Presence of the micro- and mesopores resulted in higher specific surface area (SSA), enhanced solubility, i.e., ion release, and, accordingly, increase in the amount of BSA adsorbed on the microspheres. Furthermore, the BSA adsorption capacity of the microspheres decreased with increasing Mg content despite of higher SSA.     

Cross-thickness vibration welding of polycarbonate,polyetherimide, poly(butylene terephthalate), and modified polyphenylene oxide

In vibration welding of thermoplastics, frictional heat generated by vibrating two parts under pressure, along their common interface, is used to effect welds. In the normal, well-understood mode, the vibratory motion is along the weld seam, which is at right angles to the thickness direction for straight boundaries. But in many applications, such as in the welding of closed seams of box-like parts, this vibratory motion occurs in the part-thickness direction, so that a portion of the molten layer along the seam is exposed to the ambient air during each vibratory cycle. The resulting reduction in temperature can affect weld quality. The process phenomenology and the weld strengths of such cross-thickness vibration-welded butt joints are investigated for four neat resins. Weld amplitudes and weld pressures are shown to affect the strengths of 120-Hz welds differently. It is shown that strengths on the order of the strengths of the neat resins can be achieved in 250-Hz butt welds.     

Structure–Activity Relationships of Benzenesulfonamide‐Based Inhibitors towards Carbonic Anhydrase Isoform Specificity

Carbonic anhydrases (CAs) are implicated in a wide range of diseases, including the upregulation of isoforms CA IX and XII in many aggressive cancers. However, effective inhibition of disease‐implicated CAs should minimally affect the ubiquitously expressed isoforms, including CA I and II, to improve directed distribution of the inhibitors to the cancer‐associated isoforms and reduce side effects. Four benzenesulfonamide‐based inhibitors were synthesized by using the tail approach and displayed nanomolar affinities for several CA isoforms. The crystal structures of the inhibitors bound to a CA IX mimic and CA II are presented. Further in silico modeling was performed with the inhibitors docked into CA I and XII to identify residues that contributed to or hindered their binding interactions. These structural studies demonstrated that active‐site residues lining the hydrophobic pocket, especially positions 92 and 131, dictate the positional binding and affinity of inhibitors, whereas the tail groups modulate CA isoform specificity. Geometry optimizations were performed on each ligand in the crystal structures and showed that the energetic penalties of the inhibitor conformations were negligible compared to the gains from active‐site interactions. These studies further our understanding of obtaining isoform specificity when designing small molecule CA inhibitors.     

Gold Stabilized with Iridium on Ceria–Niobia Catalyst: Activity and Stability for CO Oxidation

Topics in Catalysis - Monometallic gold and iridium, and bimetallic gold–iridium on ceria–niobia (Nb2O5–CeO2) catalysts were synthesized by deposition–precipitation with...