The ability to direct bimetallic nanoparticles to express desirable surface composition is a crucial step toward effective heterogeneous catalysis, sensing, and bionanotechnology applications. Here ...we report surface composition tuning of bimetallic Au–Pt electrocatalysts for carbon monoxide and methanol oxidation reactions. We establish a direct correlation between the surface composition of Au–Pt nanoparticles and their catalytic activities. We find that the intrinsic activities of Au–Pt nanoparticles with the same bulk composition of Au0.5Pt0.5 can be enhanced by orders of magnitude by simply controlling the surface composition. We attribute this enhancement to the weakened CO binding on Pt in discrete Pt or Pt-rich clusters surrounded by surface Au atoms. Our finding demonstrates the importance of surface composition control at the nanoscale in harnessing the true electrocatalytic potential of bimetallic nanoparticles and opens up strategies for the development of highly active bimetallic nanoparticles for electrochemical energy conversion.
Existing additively manufactured aluminum alloys exhibit poor creep resistance due to coarsening of their strengthening phases and refined grain structures. In this paper, we report on a novel ...additively manufactured Al-10.5Ce-3.1Ni-1.2Mn wt.% alloy which displays excellent creep resistance relative to cast high-temperature aluminum alloys at 300–400 °C. The creep resistance of this alloy is attributed to a high volume fraction (∼35%) of submicron intermetallic strengthening phases which are coarsening-resistant for hundreds of hours at 350 °C. The results herein demonstrate that additive manufacturing provides opportunities for development of creep-resistant aluminum alloys that may be used in bulk form in the 250–400 °C temperature range. Pathways for further development of such alloys are identified.
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The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary ...widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO
) of different microstructures and solid impurity contents using FeCl
. Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1-2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO
) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO
grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.
Li-rich layered oxides hold great promise for improving the energy density of present-day Li-ion batteries. Their application is, however, limited by the voltage decay upon cycling, and the origin of ...such a phenomenon is poorly understood. A major issue is determining the voltage range over which detrimental reactions originate. In the present study, a unique yet effective approach was employed to probe this issue. Instead of studying the materials during the first cycle, electrochemical behavior and evolution of the atomic structures were compared in extensively cycled specimens under varied charge/discharge voltages. With the upper cutoff voltage lowered from 4.8 to 4.4 V, the voltage decay ceased to occur even after 60 cycles. In the meantime, the material maintained its layered structure without any spinel phase emerging at the surface, which is unambiguously shown by the atomic-resolution Z-contrast imaging and electron energy loss spectroscopy. These results have conclusively demonstrated that structural/chemical changes responsible for the voltage decay began between 4.4 and 4.8 V, where the layered-to-spinel transition was the most dramatic structural change observed. This discovery lays important groundwork for the mechanistic understanding of the voltage decay in Li-rich layered cathode materials.
The first part of this study documented the as-aged microstructure of five cast aluminum alloys namely, 206, 319, 356, A356, and A356+0.5Cu, that are used for manufacturing automotive cylinder heads ...(Roy
et al.
in Metall Mater Trans A,
2016
). In the present part, we report the mechanical response of these alloys after they have been subjected to various levels of thermal exposure. In addition, the thermophysical properties of these alloys are also reported over a wide temperature range. The hardness variation due to extended thermal exposure is related to the evolution of the nano-scale strengthening precipitates for different alloy systems (Al-Cu, Al-Si-Cu, and Al-Si). The effect of strengthening precipitates (size and number density) on the mechanical response is most obvious in the as-aged condition, which is quantitatively demonstrated by implementing a strength model. Significant coarsening of precipitates from long-term heat treatment removes the strengthening efficiency of the nano-scale precipitates for all these alloys systems. Thermal conductivity of the alloys evolve in an inverse manner with precipitate coarsening compared to the strength, and the implications of the same for the durability of cylinder heads are noted.
Although there are only a few known examples of supported single-atom catalysts, they are unique because they bridge the gap between homogeneous and heterogeneous catalysis. Here, we report the CO ...oxidation activity of monodisperse single Pt atoms supported on an inert substrate, θ-alumina (Al2O3), in the presence of stoichiometric oxygen. Since CO oxidation on single Pt atoms cannot occur via a conventional Langmuir–Hinshelwood scheme (L–H scheme) which requires at least one Pt–Pt bond, we carried out a first-principles density functional theoretical study of a proposed pathway which is a variation on the conventional L–H scheme and inspired by the organometallic chemistry of platinum. We find that a single supported Pt atom prefers to bond to O2 over CO. CO then bonds with the oxygenated Pt atom and forms a carbonate which dissociates to liberate CO2, leaving an oxygen atom on Pt. Subsequent reaction with another CO molecule regenerates the single-atom catalyst. The energetics of the proposed mechanism suggests that the single Pt atoms will get covered with CO3 unless the temperature is raised to eliminate CO2. We find evidence for CO3 coverage at room temperature supporting the proposed mechanism in an in situ diffuse reflectance infrared study of CO adsorption on the catalyst’s supported single atoms. Thus, our results clearly show that supported Pt single atoms are catalytically active and that this catalytic activity can occur without involving the substrate. Characterization by electron microscopy and X-ray absorption studies of the monodisperse Pt/θ-Al2O3 are also presented.
Despite the maximized metal dispersion offered by single-atom catalysts, further improvement of intrinsic activity can be hindered by the lack of neighboring metal atoms in these systems. Here we ...report the use of isolated Pt
atoms on ceria as "seeds" to develop a Pt-O-Pt ensemble, which is well-represented by a Pt
O
model cluster that retains 100% metal dispersion. The Pt atom in the ensemble is 100-1000 times more active than their single-atom Pt
/CeO
parent in catalyzing the low-temperature CO oxidation under oxygen-rich conditions. Rather than the Pt-O-Ce interfacial catalysis, the stable catalytic unit is the Pt-O-Pt site itself without participation of oxygen from the 10-30 nm-size ceria support. Similar Pt-O-Pt sites can be built on various ceria and even alumina, distinguishable by facile activation of oxygen through the paired Pt-O-Pt atoms. Extending this design to other reaction systems is a likely outcome of the findings reported here.
Catalysis by single isolated atoms of precious metals has attracted much recent interest, as it promises the ultimate in atom efficiency. Most previous reports are on reducible oxide supports. Here ...we show that isolated palladium atoms can be catalytically active on industrially relevant γ-alumina supports. The addition of lanthanum oxide to the alumina, long known for its ability to improve alumina stability, is found to also help in the stabilization of isolated palladium atoms. Aberration-corrected scanning transmission electron microscopy and operando X-ray absorption spectroscopy confirm the presence of intermingled palladium and lanthanum on the γ-alumina surface. Carbon monoxide oxidation reactivity measurements show onset of catalytic activity at 40 °C. The catalyst activity can be regenerated by oxidation at 700 °C in air. The high-temperature stability and regenerability of these ionic palladium species make this catalyst system of potential interest for low-temperature exhaust treatment catalysts.
With the right support: A Ir/Fe(OH)x catalyst was designed. The Fe(OH)x support stabilizes the metal catalyst used for the oxidation of carbon monoxide. The catalyst was highly active for the ...oxidation of carbon monoxide in the presence of excess hydrogen at room temperature and showed a wide temperature range for the total conversion of CO (see picture).
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