No Arabic abstract
The practical use of nanoparticle superlattices (NPSLs) which are of great interest as materials with designed functionalities is often limited by their lack of structural stability under various utilization conditions. Here, we report a new method for directly synthesizing NPSL fully embedded in hierarchically porous silica which provides exceptional stability and efficient pathways for reactant molecules, making the NPSL highly efficient catalyst. The superlattices made of 12 nm gold nanoparticles exhibit exceptionally high catalytic activity for CO oxidation at low temperature, showing higher activity than that of small gold nanoparticles (ca. 3 nm) supported on metal oxides. The gold NPSL also shows unprecedented stability, maintaining its structural stability and catalytic activity without any signature of degradation over a month of continuous catalytic reaction, which present one significant step forward to realizing the great potentials of gold catalysts in automotive emission control and green chemistry industry.
We present results of kinetic Monte Carlo simulations of a modified Ziff-Gulari-Barshad model for the reaction CO+O --> CO_2 on a catalytic surface. Our model includes impurities in the gas phase, CO desorption, and a modification known to eliminate the unphysical O poisoned phase. The impurities can adsorb and desorb on the surface, but otherwise remain inert. In a previous work that did not include CO desorption [G. M. Buendia and P. A. Rikvold, Phys. Rev. E, 85 031143 (2012)], we found that the impurities have very distinctive effects on the phase diagram and greatly diminish the reactivity of the system. If the impurities do not desorb, once the system reaches a stationary state, the CO_2 production disappears. When the impurities are allowed to desorb, there are regions where the CO_2 reaction window reappears, although greatly reduced. Following experimental evidence that indicates that temperature effects are crucial in many catalytic processes, here we further analyze these effects by including a CO desorption rate. We find that the CO desorption has the effect to smooth the transition between the reactive and the CO rich phase, and most importantly it can counteract the negative effects of the presence of impurities by widening the reactive window such that now the system remains catalytically active in the whole range of CO pressures.
We demonstrate an organic memory-transistor device based on a pentacene-gold nanoparticles active layer. Gold (Au) nanoparticles are immobilized on the gate dielectric (silicon dioxide) of a pentacene transistor by an amino-terminated self-assembled monolayer. Under the application of writing and erasing pulses on the gate, large threshold voltage shift (22 V) and on/off drain current ratio of ~3E4 are obtained. The hole field-effect mobility of the transistor is similar in the on and off states (less than a factor 2). Charge retention times up to 4500 s are observed. The memory effect is mainly attributed to the Au nanoparticles.
We report the investigation of the generation and detection of GHz coherent acoustic phonons in plasmonic gold nanoparticles superlattices (NPS). The experiments have been performed from an optical femtosecond pump-probe scheme across the optical plasmon resonance of the superlattice. Our experiments allow to estimate the collective elastic response (sound velocity) of the NPS as well as an estimate of the nano-contact elastic stiffness. It appears that the light-induced coherent acoustic phonon pulse has a typical in-depth spatial extension of about 45 nm which is roughly 4 times the optical skin depth in gold. The modeling of the transient optical reflectivity indicates that the mechanism of phonon generation is achieved through ultrafast heating of the NPS assisted by light excitation of the volume plasmon. These results demonstrate how it is possible to map the photon-electron-phonon interaction in subwavelength nanostructures.
The imaging of active nanoparticles represents a milestone in decoding heterogeneous catalysts dynamics. We report the facet resolved, surface strain state of a single PtRh alloy nanoparticle on SrTiO3 determined by coherent x-ray diffraction imaging under catalytic reaction conditions. Density functional theory calculations allow us to correlate the facet surface strain state to its reaction environment dependent chemical composition. We find that the initially Pt terminated nanoparticle surface gets Rh enriched under CO oxidation reaction conditions. The local composition is facet orientation dependent and the Rh enrichment is non-reversible under subsequent CO reduction. Tracking facet resolved strain and composition under operando conditions is crucial for a rational design of more efficient heterogeneous catalysts with tailored activity, selectivity and lifetime.
Silica is known as the archetypal strong liquid, exhibiting an Arrhenius viscosity curve with a high glass transition temperature and constant activation energy. However, given the ideally isostatic nature of the silica network, the presence of even a small concentration of defects can lead to a significant decrease in both the glass transition temperature and activation energy for viscous flow. To understand the impact of trace level dopants on the viscosity of silica, we measure the viscosity-temperature curves for seven silica glass samples having different impurities, including four natural and three synthetic samples. Depending on the type of dopant, the glass transition temperature can vary by nearly 300 K. A common crossover is found for all viscosity curves around ~2200-2500 K, which we attribute to a change of the transport mechanism in the melt from being dominated by intrinsic defects at high temperature to dopant-induced defects at low temperatures.