Au-Pd separation enhances bimetallic catalysis of alcohol oxidation.

In oxidation reactions catalysed by supported metal nanoparticles with oxygen as the terminal oxidant, the rate of the oxygen reduction can be a limiting factor. This is exemplified by the oxidative dehydrogenation of alcohols, an important class of reactions with modern commercial applications1-3. Supported gold nanoparticles are highly active for the dehydrogenation of the alcohol to an aldehyde4 but are less effective for oxygen reduction5,6. By contrast, supported palladium nanoparticles offer high efficacy for oxygen reduction5,6. This imbalance can be overcome by alloying gold with palladium, which gives enhanced activity to both reactions7,8,9; however, the electrochemical potential of the alloy is a compromise between that of the two metals, meaning that although the oxygen reduction can be improved in the alloy, the dehydrogenation activity is often limited. Here we show that by separating the gold and palladium components in bimetallic carbon-supported catalysts, we can almost double the reaction rate compared with that achieved with the corresponding alloy catalyst. We demonstrate this using physical mixtures of carbon-supported monometallic gold and palladium catalysts and a bimetallic catalyst comprising separated gold and palladium regions. Furthermore, we demonstrate electrochemically that this enhancement is attributable to the coupling of separate redox processes occurring at isolated gold and palladium sites. The discovery of this catalytic effect-a cooperative redox enhancement-offers an approach to the design of multicomponent heterogeneous catalysts.

Benzyl alcohol oxidation with Pd-Zn/TiO2: computational and experimental studies.

Pd-Zn/TiO2 catalysts containing 1 wt% total metal loading, but with different Pd to Zn ratios, were prepared using a modified impregnation method and tested in the solvent-free aerobic oxidation of benzyl alcohol. The catalyst with the higher Pd content exhibited an enhanced activity for benzyl alcohol oxidation. However, the selectivity to benzaldehyde was significantly improved with increasing presence of Zn. The effect of reduction temperature on catalyst activity was investigated for the catalyst having a Pd to Zn metal molar ratio of 9:1. It was found that lower reduction temperature leads to the formation of PdZn nanoparticles with a wide particle size distribution. In contrast, smaller PdZn particles were formed upon catalyst reduction at higher temperatures. Computational studies were performed to compare the adsorption energies of benzyl alcohol and the reaction products (benzaldehyde and toluene) on PdZn surfaces to understand the oxidation mechanism and further explain the correlation between the catalyst composition and its activity.

Activation and Deactivation of Gold/Ceria-Zirconia in the Low-Temperature Water-Gas Shift Reaction.

Gold (Au) on ceria-zirconia is one of the most active catalysts for the low-temperature water-gas shift reaction (LTS), a key stage of upgrading H2 reformate streams for fuel cells. However, this catalyst rapidly deactivates on-stream and the deactivation mechanism remains unclear. Using stop-start scanning transmission electron microscopy to follow the exact same area of the sample at different stages of the LTS reaction, as well as complementary X-ray photoelectron spectroscopy, we observed the activation and deactivation of the catalyst at various stages. During the heating of the catalyst to reaction temperature, we observed the formation of small Au nanoparticles (NPs; 1-2 nm) from subnanometer Au species. These NPs were then seen to agglomerate further over 48 h on-stream, and most rapidly in the first 5 h when the highest rate of deactivation was observed. These findings suggest that the primary deactivation process consists of the loss of active sites through the agglomeration and possible dewetting of Au NPs.

Optimization of physical and dielectric properties of Co-doped ZnO nanoparticles for low-frequency devices.

In this study, zinc-oxide (ZnO) nanoparticles (NPs) doped with cobalt (Co) were synthesized using a simple coprecipitation technique. The concentration of Co was varied to investigate its effect on the structural, morphological, optical, and dielectric properties of the NPs. X-ray diffraction (XRD) analysis confirmed the hexagonal wurtzite structure of both undoped and Co-doped ZnO-NPs. Scanning electron microscopy (SEM) was used to examine the morphology of the synthesized NPs, while energy-dispersive X-ray spectroscopy (EDX) was used to verify their purity. The band gap of the NPs was evaluated using UV-visible spectroscopy, which revealed a decrease in the energy gap as the concentration of Co2+ increased in the ZnO matrix. The dielectric constants and AC conductivity of the NPs were measured using an LCR meter. The dielectric constant of the Co-doped ZnO-NPs continuously increased from 4.0 × 10-9 to 2.25 × 10-8, while the dielectric loss decreased from 4.0 × 10-8 to 1.7 × 10-7 as the Co content increased from 0.01 to 0.07%. The a.c. conductivity also increased with increasing applied frequency. The findings suggest that the synthesized Co-doped ZnO-NPs possess enhanced dielectric properties and reduced energy gap, making them promising candidates for low-frequency devices such as UV photodetectors, optoelectronics, and spintronics applications. The use of a cost-effective and scalable synthesis method, coupled with detailed material characterization, makes this work significant in the field of nanomaterials and device engineering.

The Effect of Reinforcement Preheating Temperatures on Tribological Behavior of Advanced Quranic Metal-Matrix Composites (QMMC).

The growing applications of iron/copper bimetallic composites in various industries are increasing. The relationship between the properties of these materials and manufacturing parameters should be well understood. This paper represents an experimental study to evaluate the effect of reinforcement (steel rod) preheating temperature on the mechanical properties (bond strength, microhardness, and wear resistance) of copper matrix composites (QMMC). In preparing the QMMC samples, the melted copper was poured on a steel rod that had been preheated to various temperatures, namely, room temperature, 600 °C, 800 °C, and 1200 °C. Properties of the QMMC (interface microstructure, interfacial bonding strength, microhardness, and wear) were investigated. The experimental results revealed that the best bond between the copper matrix and steel rod formed only in the composites prepared by preheating the steel rods with temperatures lower than the recrystallization temperature of steel (723 °C). This is because the oxide layer and shrinkage voids (due to the difference in shrinkage between the two metals) at the interface hinder atom diffusion and bond formation at higher temperatures. The microhardness test showed that preheating steel rod to 600 °C gives the highest value among all the samples. Furthermore, the QMMC's wear behavior confirmed that the optimization of preheating temperature is 600 °C.

Mechanical and Tribological Behavior of Functionally Graded Unidirectional Glass Fiber-Reinforced Epoxy Composites.

This paper aims to assess experimentally the mechanical and tribological behavior of conventional and functionally graded (FG) polymeric matrix composites reinforced with continuous glass fibers. The small punch test (SPT) and a pin-on-disc device were used in the present work to examine the mechanical and wear behavior, respectively. The hand lay-up technique was used in the present investigation to manufacture the conventional and FG composites. Various wooden looms with different nailed spacing were employed to manufacture the FG composites. According to test type, the FG composite is composed of four and ten layers, with a different glass fiber volume of fraction (Vf%) for each layer. In addition, the finite element simulation based on Hashin's failure criterion and cohesive zone modeling was used to show the progressive failure and give more explanation regarding the flexural behavior of such composites. The present results indicate that the wear rate of an FG composite could be affected by many factors, including the disk speed, applied load, the composite layers number, and average glass fiber volume fraction. On the other hand, the arrangement of layers in the composite materials by variation of Vf% for each layer can improve the wear rate and value of the ultimate load before the fracture of the composite material when subjected to SPT. The experimental and numerical results for all SPT specimens showed that the fracture of the SPT specimens began beneath the punch tip and grew along the fiber direction. The ultimate flexural capacity of FG composites increased by 30% compared with the conventional composites.

Synthesis of highly uniform and composition-controlled gold-palladium supported nanoparticles in continuous flow.

The synthesis of supported bimetallic nanoparticles with well-defined size and compositional parameters has long been a challenge. Although batch colloidal methods are commonly used to pre-form metal nanoparticles with the desired size-range in solution, inhomogeneous mixing of the reactant solutions often leads to variations in size, structure and composition from batch-to-batch and even particle-to-particle. Here we describe a millifluidic approach for the production of oxide supported monometallic Au and bimetallic AuPd nanoparticles in a continuous fashion. This optimised method enables the production of nanoparticles with smaller mean sizes, tighter particle size distributions and a more uniform particle-to-particle chemical composition as compared to the conventional batch procedure. In addition, we describe a facile procedure to prepare bimetallic Au@Pd core-shell nanoparticles in continuous flow starting from solutions of the metal precursors. Moreover, the relative ease of scalability of this technique makes the proposed methodology appealing not only for small-scale laboratory purposes, but also for the industrial-scale production of supported metal nanoparticles.

Aqueous Au-Pd colloids catalyze selective CH4 oxidation to CH3OH with O2 under mild conditions.

The selective oxidation of methane, the primary component of natural gas, remains an important challenge in catalysis. We used colloidal gold-palladium nanoparticles, rather than the same nanoparticles supported on titanium oxide, to oxidize methane to methanol with high selectivity (92%) in aqueous solution at mild temperatures. Then, using isotopically labeled oxygen (O2) as an oxidant in the presence of hydrogen peroxide (H2O2), we demonstrated that the resulting methanol incorporated a substantial fraction (70%) of gas-phase O2 More oxygenated products were formed than the amount of H2O2 consumed, suggesting that the controlled breakdown of H2O2 activates methane, which subsequently incorporates molecular oxygen through a radical process. If a source of methyl radicals can be established, then the selective oxidation of methane to methanol using molecular oxygen is possible.

Synergy and Anti-Synergy between Palladium and Gold in Nanoparticles Dispersed on a Reducible Support.

Highly active and stable bimetallic Au-Pd catalysts have been extensively studied for several liquid-phase oxidation reactions in recent years, but there are far fewer reports on the use of these catalysts for low-temperature gas-phase reactions. Here we initially established the presence of a synergistic effect in a range of bimetallic Au-Pd/CeZrO4 catalysts, by measuring their activity for selective oxidation of benzyl alcohol. The catalysts were then evaluated for low-temperature WGS, CO oxidation, and formic acid decomposition, all of which are believed to be mechanistically related. A strong anti-synergy between Au and Pd was observed for these reactions, whereby the introduction of Pd to a monometallic Au catalyst resulted in a significant decrease in catalytic activity. Furthermore, monometallic Pd was more active than Pd-rich bimetallic catalysts. The nature of the anti-synergy was probed by several ex situ techniques, which all indicated a growth in metal nanoparticle size with Pd addition. However, the most definitive information was provided by in situ CO-DRIFTS, in which CO adsorption associated with interfacial sites was found to vary with the molar ratio of the metals and could be correlated with the catalytic activity of each reaction. As a similar correlation was observed between activity and the presence of Au0* (as detected by XPS), it is proposed that peripheral Au0* species form part of the active centers in the most active catalysts for the three gas-phase reactions. In contrast, the active sites for the selective oxidation of benzyl alcohol are generally thought to be electronically modified gold atoms at the surface of the nanoparticles.