Single entity electrochemistry and the electron transfer kinetics of hydrazine oxidation

The mechanism and kinetics of the electro-catalytic oxidation of hydrazine by graphene oxide platelets randomly decorated with palladium nanoparticles are deduced using single particle impact electrochemical measurements in buffered aqueous solutions across the pH range 2–11. Both hydrazine, N2H4, and protonated hydrazine N2H5+ are shown to be electroactive following Butler-Volmer kinetics, of which the relative contribution is strongly pH-dependent. The negligible interconversion between N2H4 and N2H5+ due to the sufficiently short timescale of the impact voltammetry, allows the analysis of the two electron transfer rates from impact signals thus reflecting the composition of the bulk solution at the pH in question. In this way the rate determining step in the oxidation of each specie is deduced to be a one electron step in which no protons are released and so likely corresponds to the initial formation of a very short-lived radical cation either in solution or adsorbed on the platelet. Overall the work establishes a generic method for the elucidation of the rate determining electron transfer in a multistep process free from any complexity imposed by preceding or following chemical reactions which occur on the timescale of conventional voltammetry.

Multiscale Material Characterization Based on Single Particle Impact Utilizing Particle-Oriented Peening and Single-Impact Peening

If conventional methods are used, the development of new structural materials is experience-based, but still intensive in terms of materials, time and cost. As part of the development of a new method for material development and characterization, particle-oriented peening is used in this work. By means of samples of different sizes—but matching microstructures (100Cr6 (AISI 52100), five different material states)—it is examined whether the quantities determined on microscopic samples can be transferred to macroscopic samples. Therefore, peening processes with matching peening parameters but different deformation related aims are compared. While the particle-oriented peening is used to deform the microscopic samples (d = 0.8 mm), the new method of single-impact peening is used to deform the macroscopic samples. For the cross-scale comparison, values characterizing the plastic material deformation (∆l and rf, rc) are used as well as the particle velocities after the impact influenced by the elasto-plastic material properties. It could be shown that the highly dynamic (material) behavior is comparable in both dimensions. For the future examination of new (unknown) material states it is therefore conceivable to make predictions regarding their material behavior and later on regarding their material properties on the basis of particle-oriented peening of quickly generated microscopic samples e.g., from drop-on-demand processes.