Dissolution Heterogeneity Observed in Anisotropic Ruthenium Dioxide Nanocrystals via Liquid-Phase Transmission Electron Microscopy.

Noble metal oxides such as ruthenium dioxide are highly active electrocatalysts for anodic reactions in acidic electrolytes, but dissolution during electrochemical operation impedes wide-scale applications in renewable energy technologies. Improving the fundamental understanding of the dissolution dynamics of application-relevant morphologies such as nanocrystals is critical for the grid-scale implementation of these materials. Herein, we report the nanoscale heterogeneity observed via liquid-phase transmission electron microscopy during ruthenium dioxide nanocrystal dissolution under oxidizing conditions.

Facet-selective etching trajectories of individual semiconductor nanocrystals.

The size and shape of semiconductor nanocrystals govern their optical and electronic properties. Liquid cell transmission electron microscopy (LCTEM) is an emerging tool that can directly visualize nanoscale chemical transformations and therefore inform the precise synthesis of nanostructures with desired functions. However, it remains difficult to controllably investigate the reactions of semiconductor nanocrystals with LCTEM, because of the highly reactive environment formed by radiolysis of liquid.

Redox Mediated Control of Electrochemical Potential in Liquid Cell Electron Microscopy.

Liquid cell electron microscopy enables the study of nanoscale transformations in solvents with high spatial and temporal resolution, but for the technique to achieve its potential requires a new level of control over the reactivity caused by radical generation under electron beam irradiation. An understanding of how to control electron-solvent interactions is needed to further advance the study of structural dynamics for complex materials at the nanoscale. We developed an approach that scavenges radicals with redox species that form well-defined redox couples and control the electrochemical potential .

In Situ Quantification of Interactions between Charged Nanorods in a Predefined Potential Energy Landscape.

Quantitative understanding of nanoscale interactions is a prerequisite for harnessing the remarkable collective properties of nanoparticle systems. Here, we report the combined use of liquid-phase transmission electron microscopy and electron beam lithography to elucidate the interactions between charged nanorods in a predefined potential energy landscape. In situ site-selective lift-off of surface-functionalized lithographed gold nanorods is achieved by patterning them with adhesion layer materials that undergo etching at different rates.

Precise Colloidal Plasmonic Photocatalysts Constructed by Multistep Photodepositions.

Natural photosynthesis relies on a sophisticated charge transfer pathway among multiple components with precise spatial, energetic, and temporal organizations in the aqueous environment. It continues to inspire and challenge the design and fabrication of artificial multicomponent colloidal nanostructures for solar-to-fuel conversion. Herein, we introduce a plasmonic photocatalyst synthesized with colloidal methods with five integrated components including cocatalysts installed in orthogonal locations.

Self-Limiting Shell Formation in Cu@Ag Core-Shell Nanocrystals during Galvanic Replacement.

The understanding of synthetic pathways of bimetallic nanocrystals remains limited due to the complex energy landscapes and dynamics involved. In this work, we investigate the formation of self-limiting Cu@Ag core-shell nanoparticles starting from Cu nanocrystals followed by galvanic replacement with Ag ions. Bulk quantification with atomic emission spectroscopy and spatially resolved elemental mapping with electron microscopy reveal distinct nucleation regimes that produce nanoparticles with a tunable Ag shell thickness, but only up to a certain limiting thickness.

Photoelectrochemical Behavior of a Molecular Ru-Based Water-Oxidation Catalyst Bound to TiO-Protected Si Photoanodes.

A hybrid photoanode based on a molecular water oxidation precatalyst was prepared from TiO-protected n- or p-Si coated with multiwalled carbon nanotubes (CNT) and the ruthenium-based water oxidation precatalyst [Ru(tda)(py-pyr)(O)], 1(O) (tda is [2,2':6',2″-terpyridine]-6,6″-dicarboxylato and py-pir is 4-(pyren-1-yl)-N-(pyridin-4-ylmethyl)butanamide). The Ru complex was immobilized by π-π stacking onto CNTs that had been deposited by drop casting onto Si electrodes coated with 60 nm of amorphous TiO and 20 nm of a layer of sputtered C. At pH = 7 with 3 Sun illumination, the n-Si/TiO/C/CNT/[1+1(O)] electrodes exhibited current densities of 1 mA cm at 1.