Alloying is well-known to improve the dehydrogenation selectivity of pure metals, but there remains considerable debate about the structural and electronic features of alloy surfaces that give rise to this behavior. To provide molecular-level insights into these effects, a series of Pd intermetallic alloy catalysts with Zn, Ga, In, Fe and Mn promoter elements was synthesized, and the structures were determined using in situ X-ray absorption spectroscopy (XAS) and synchrotron X-ray diffraction (XRD). The alloys all showed propane dehydrogenation turnover rates 5–8 times higher than monometallic Pd and selectivity to propylene of over 90%. Moreover, among the synthesized alloys, Pd 3 M alloy structures were less olefin selective than PdM alloys which were, in turn, almost 100% selective to propylene. This selectivity improvement was interpreted by changes in the DFT-calculated binding energies and activation energies for C–C and C–H bond activation, which are ultimately influenced by perturbation of the most stable adsorption site and changes to the d-band density of states. Furthermore, transition state analysis showed that the C–C bond breaking reactions require 4-fold ensemble sites, which are suggested to be required for non-selective, alkane hydrogenolysis reactions. These sites, which are not present on alloys with PdM structures, could bemore »
Corrosion Behavior and Hardness of Binary Mg Alloys Produced via High-Energy Ball-Milling and Subsequent Spark Plasma Sintering
In this work, nine nanocrystalline binary Mg alloys were synthesized by high-energy ball milling. The compositions, Mg-5 wt% M (M-Cr, Ge, Mn, Mo, Ta, Ti, V, Y, and Zn), were milled with the objective of achieving non-equilibrium alloying. The milled alloys were consolidated via cold compaction (CC) at 25°C and spark plasma sintering (SPS) at 300°C. X-ray diffraction (XRD) analysis indicated grain refinement below 100 nm, and the scanning electron microscopy revealed homogeneous microstructures for all compositions. XRD analysis revealed that most of the alloys showed a change in the lattice parameter, which indicates the formation of a solid solution. A significant increase in the hardness compared to unmilled Mg was observed for all of the alloys. The corrosion behavior was improved in all of the binary alloys compared to milled Mg. A significant decrease in the cathodic kinetics was evident due to Ge and Zn additions. The influence of the alloying elements on corrosion behavior has been categorized and discussed based on the electrochemical response of their respective binary Mg alloys.
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- 228 to 241
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- National Science Foundation
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