Ordered arrays of low-dimensional Au and Pd : synthesis and in situ observations

Abstract: Electrodeposition of metals in templates of nano-porous anodic aluminum oxide (NP-AAO) is a versatile way of fabricating ordered arrays of metal nanowires. Thanks to the self-arranged long-range hexagonal order of the pores, electrodeposition in NP-AAO is an easily scalable bottom-up synthesis route and an attractive alternative to traditional top-down fabrication methods such as electron beam lithography.Since NP-AAO is a non-conductive medium and since it is potentially soluble in non-neutral pH solutions, the electrodeposition of metals in NP-AAO represents a challenge. These aspects are discussed in this thesis, aiming to establish a reproducible and reliable protocol for the electrodeposition of Au and Pd.By using ex situ x-ray diffraction, it has been found that the growth of Au and Pd in the confined environment of nano-pores leads (i) to a deformation of the crystalline structure, as the lattice constant is smaller along the nanowire radius and larger along the nanowire axis, compared to the bulk lattice constant, and (ii) to a crystallite size anisotropy: it is limited by the pore radius in the horizontal direction and it is larger in the direction of growth.The electrochemical growth of Au and Pd nanowires was followed in situ by x-ray scattering methods. In the case of Au nanowires, the time-resolved measurements revealed that the anisotropy of the lattice parameter progresses as a function of time, which suggests that the strain state of the nanomaterials can be artificially selected. This findings might be beneficial in the strain-engineering of Au nanoelectrode arrays for electrocatalysis. In the case of Pd nanowires, the measurements revealed strain variations, as well as phase transitions attributed to the existence of alpha- and beta-phase Pd hydride in the NP-AAO template, due to the exposure of Pd to hydrogen evolved at the working electrode. These findings suggest that Pd in NP-AAO has potential applications in the design of hydrogen storage devices.