Enabling near-atomic-scale analysis of frozen water.

Transmission electron microscopy went through a revolution enabling routine cryo-imaging of biological and (bio)chemical systems, in liquid form. Yet, these approaches typically lack advanced analytical capabilities. Here, we used atom probe tomography to analyze frozen liquids in three dimensions with subnanometer resolution. We introduce a specimen preparation strategy using nanoporous gold. We report data on 2- to 3-µm-thick layers of ice formed from both high-purity deuterated water and a solution of 50 mM NaCl in high-purity deuterated water. The analysis of the gold-ice interface reveals a substantial increase in the solute concentrations across the interface. We explore a range of experimental parameters to show that atom probe analyses of bulk aqueous specimens come with their own challenges and discuss physical processes that produce the observed phenomena. Our study demonstrates the viability of using frozen water as a carrier for near-atomic-scale analysis of objects in solution by atom probe tomography.

Nanoscale mechanism of the stabilization of nanoporous gold by alloyed platinum.

Nanoporous gold (NPG) is usually made by electrochemical dealloying of Ag from binary AgAu alloys. The resulting nanoscale ligaments are not very stable, and tend to coarsen with time by surface self-diffusion, especially in electrolyte, which may lead to inferior electrocatalytic properties. Addition of a small amount of Pt to the precursor alloy is known to refine and stabilize the nanoporous product (NPG-Pt). However, the mechanisms by which Pt serves to refine the microstructure remain poorly understood. The present study aims to expand our knowledge of the role of Pt by examining NPG-Pt at atomic resolution with Atom Probe Tomography (APT), as well as by aberration-corrected Transmission Electron Microscopy. Atomic level observation of Pt enrichment on ligament surfaces sheds light on the underlying mechanisms that give rise to Pt's refining effect. Owing to improved Ag retention with higher Pt content, NPG-Pt1 (made by dealloying Ag77Au22Pt1) was shown to have the highest surface area-to-volume ratio, compared to NPG-Pt3 (made by dealloying Ag77Au20Pt3). Quantitative estimates reveal up to 5-fold enrichment of Pt at nanoligament surfaces, compared to the precursor content, in NPG-Pt. The interface between the dealloyed layer and the substrate was captured by APT, for the first time. The findings of this investigation add insight into the functionality of NPG-Pt and its prospective catalytic performance.