Impact of surface mechanics on the reactivity of electrodes.

Theory links the reactivity of metal surfaces to the interatomic spacing and, hence, to the tangential strain. We point out that this proposition can be experimentally verified by exploiting a seemingly unrelated phenomenon, the mechanical deformation of solid bodies when charged in an electrolyte. Such experiments allow the strength of coupling between adsorption enthalpy and strain to be quantified. For hydrogen adsorption on Pd, the result agrees with ab initio computation and with trends that can be inferred from experiment on pseudomorphic layers strained by epitaxy with misfitting substrates. The data suggest that experimentally accessible strain values afford a variation of the adatom concentration by several orders of magnitude and a significant shift of the reaction along the 'volcano curve' of reactivity versus adsorption strength.

Surface-chemistry-driven actuation in nanoporous gold.

Although actuation in biological systems is exclusively powered by chemical energy, this concept has not been realized in man-made actuator technologies, as these rely on generating heat or electricity first. Here, we demonstrate that surface-chemistry-driven actuation can be realized in high-surface-area materials such as nanoporous gold. For example, we achieve reversible strain amplitudes of the order of a few tenths of a per cent by alternating exposure of nanoporous Au to ozone and carbon monoxide. The effect can be explained by adsorbate-induced changes of the surface stress, and can be used to convert chemical energy directly into a mechanical response, thus opening the door to surface-chemistry-driven actuator and sensor technologies.

Potential/charge induced nanoporous metal actuators.

The mechanical response to the electrochemical charging of nanoporous metals with their pore space wetted by electrolyte have been studied in-situ using dilatometry and wide angle x-ray diffractometry techniques. The actuation strain reported in this manuscript is purely elastic and completely reversible. The capacitive double layer charging became more effective near to the potential to zero charge (pzc) and contribute significantly to the variations of surface stress and crystal strain. In a suitable experimental setup, the actuator effect from porous metals can be amplified, where deliberate movements of the actuator parts are desirable with minimum external force, suggesting that metallic foam-like materials with high surface to volume ratio could be used to mimic natural muscles.

Surface stress-charge response of a (111)-textured gold electrode under conditions of weak ion adsorption.

We report a cantilever bending investigation into the variation of surface stress, f, with surface charge density, q, for (111)-textured thin films of gold in aqueous NaF and HClO 4. The graphs of f(q) are highly linear, and the surface stress-charge coefficients, d f/d q, are -1.95 V for 7 mM NaF and -2.0 V for 10 mM HClO 4 near the potential of zero charge. These values exceed some previously published experimental data by a factor of 2, but they agree with recent ab initio calculations of the surface stress-charge response of gold in vacuum.

Variation of the surface stress-charge coefficient of platinum with electrolyte concentration.

We report an experimental study of the variation of surface stress with surface charge density for nanoporous Pt immersed in aqueous solutions of NaF of various concentration. As the concentration is reduced, we find initially an increase in the magnitude of the surface stress-charge coefficient, followed by saturation at a value of -1.9 V. Since specific adsorption is expected to be reduced as the solution becomes more dilute, the results support the notion that changes in the bonding at the metal surface play a decisive role in determining the change in the surface stress during double-layer charging.

Range of magnetic correlations in nanocrystalline soft magnets.

We have obtained the magnetic field dependence of static ferromagnetic correlations in nanocrystalline electrodeposited Co and Ni by means of the correlation function of the spin misalignment, determined from small-angle neutron scattering data. The approach yields a correlation length l(C), which is a measure for the spatial extent of inhomogeneities in the magnetization distribution. The correlation length depends strongly on the applied magnetic field with values ranging from 94 nm in nanocrystalline Co at low fields to about 15 nm at saturation. The results for l(C) indicate that in Co the main source of nonuniformity in the spin system is the anisotropy field of each individual crystallite, whereas in nanocrystalline Ni the main sources of spin disorder originate from twin faults or from the defect cores of grain boundaries.

Charge-induced reversible strain in a metal.

Dimension changes on the order of 0.1% or above in response to an applied voltage have been reported for many types of materials, including ceramics, polymers, and carbon nanostructures, but not, so far, for metals. We show that reversible strain amplitudes comparable to those of commercial piezoceramics can be induced in metals by introducing a continuous network of nanometer-sized pores with a high surface area and by controlling the surface electronic charge density through an applied potential relative to an electrolyte impregnating the pores.