A novel analytical methodology based on correlated optical and electroanalytical measurements was developed to probe electrocatalytic reactions at individual nanoparticles (NPs) with well-defined geometries. The developed methodology, Optically Targeted ElectroChemical Cell Microscopy (OTECCM), relies on a combination of optical hyperspectral imaging, to locate individual NPs and provide structural information, and Scanning ElectroChemical Cell Microscopy (SECCM), to provide direct information on the electrochemical behavior of the same NPs. This complementary strategy allows for SECCM measurements to be carried out in a "targeted" fashion, offering significant throughput advantages over conventional, scanning-based approaches. The developed methodology was applied to study the electrocatalytic oxidation of hydrazine at individual Au nanorods (NRs). Correlated electron microscopy investigations were carried out to conclusively demonstrate the ability of the proposed methodology to probe electrochemical reactions at individual NRs. A wide variety in behavior of the individual NRs was observed, with surface reactions at Au playing a prominent role in the observed response. In situ spectroscopic investigations at individual NRs suggest surface restructuring and/or residual ligand desorption leads to significant changes in catalytic activity over time. Results from the correlated electron microscopy investigations as well as the statistical analyses of data obtained for hundreds of individual nanostructures suggest that the gross geometry of a NR is a poor predictor of its electrocatalytic performance.
Spatial variations in photoelectrochemical reaction rates within individual p-type WSe2 nanosheets were mapped through the application of scanning electrochemical cell microscopy (SECCM). The simultaneous topographical and electrochemical information provided via SECCM directly revealed how both sheet thickness and the presence of defect structures affect the local rate of photoelectrochemical reactions for both outer sphere and inner sphere redox couples. Sheet thickness was found to play a dramatic role in reaction rates, with onset potentials shifting by as much as 0.5 V over thicknesses of 20–120 nm, attributable to the inability of thin sheets to support independent space charge layers. Step/edge features were found to play a detrimental role for the outer sphere redox couple investigated (Ru(NH3)6 3+ reduction), with taller steps having larger effects on performance. Shorter step features were found to be beneficial for hydrogen evolution, showing a controlled density of defect features is desirable for inner sphere processes. The studies presented here not only provide valuable, quantitative insights into the behavior of transitional metal dichalcogenide materials but also demonstrate the power of applying SECCM to the study of photoelectrochemical systems, particularly those involving two-dimensional (2D) materials.
Two-dimensional semiconductors (2DSCs) are promising materials for a wide range of optoelectronic applications. While the fabrication of 2DSCs with thicknesses down to the monolayer limit has been demonstrated through a...
The role played by heating in the electrochemical behavior of plasmonic nanostructures under illumination was examined through a combination of theoretical modeling and experimental investigations. A theoretical treatment of heating in plasmonic electrochemical systems was developed, which treats heat flow from arrays of nanoparticles attached to an electrode as a heat source delocalized across the electrode−solution interface. Within this framework, simple analytical expressions for the temperature profile in the vicinity of illuminated electrodes are presented for a 1D model treating heat transfer via conduction. Results from more detailed finite element simulations treating heat transfer via both conduction and convection in realistic cell geometries are also provided. Both approaches predict significant increases in the mass transfer of dissolved redox species, which can readily explain the current enhancements observed with electrodes decorated with plasmonic nanostructures under illumination. These predictions were tested experimentally by employing conventional, millimeter-sized electrodes decorated with Au nanoparticles in potential step experiments under intermittent illumination. Experiments with both outer-sphere (ferrocene methanol) and inner-sphere (hydrazine) redox couples displayed significant current enhancements due to illumination, which agreed well with theoretical predictions. Experiments at individual nanoparticles were also carried out using probe-based techniques. These measurements displayed no significant effects due to heating, attributable to efficient heat transfer away from nanoparticles in this experimental geometry. Implications of these results on research into the effects of hot charge carriers in electrochemical experiments are discussed.
Control over photophysical and chemical properties of two-dimensional (2D) transition metal dichalcogenides (TMDs) is the key to advance their applications in next-generation optoelectronics. Although chemical doping and surface modification with plasmonic metals have been reported to tune the photophysical and catalytic properties of 2D TMDs, there have been few reports of tuning optical properties using dynamic electrochemical control of electrode potential. Herein, we report (1) the photoluminescence (PL) enhancement and red-shift in the PL spectrum of 2D MoS2, synthesized by chemical vapor deposition and subsequent transfer onto an indium tin oxide electrode, upon electrochemical anodization and (2) spatial heterogeneities in its photoelectrochemical (PEC) activities. Spectroelectrochemistry shows that positive electrochemical bias causes an initial ten-fold increase in the PL intensity followed by a quick decrease in the enhancement. The PL enhancement and spectrum red-shift are associated with the decrease in nonradiative decay rates of excitons formed upon electrochemical anodization of 2D MoS2. Additionally, scanning electrochemical cell microscopy (SECCM) study shows that the 2D MoS2 crystal is spatially sensitive to PEC oxidation at positive potentials. SECCM also shows a photocurrent increase caused by spatially heterogeneous edge-type defect sites of the crystal.
Transition metal dichalcogenides (TMDs) are attractive materials for a variety of applications in solar energy conversion and electrocatalysis, due to their favorable optical and electrical properties and their unique two-dimensional structures which facilitate the fabrication of wide-area, ultrathin layers. Unfortunately, the basal planes which make up the majority of these materials are relatively inert, and thus a great deal of effort has been directed to engineering favorable, catalytically active defects into these materials. Here, we demonstrate how probe-based electrochemical techniques can be employed as multifunctional tools for locally modifying TMD materials and probing the electrochemical behavior of the resulting defects. Scanning Electrochemical Cell Microscopy (SECCM) was employed to locally anodize exfoliated p-type WSe2 nanosheets, creating hole-like defects within individual basal planes in a highly controllable fashion. Photoelectrochemical SECCM imaging was then employed to characterize the chemical behavior of these engineered defects, revealing significantly enhanced activity toward the Hydrogen Evolution Reaction (HER). Atomic force microscopy studies are presented which suggest these enhancements result from an increased density of monolayer-high step features within the anodized defects. Analysis of the SECCM data in the context of finite element simulations revealed that these enhancements increased with increasing anodization time, with local kinetic rates over 2 orders of magnitude higher than unaltered basal planes.
Epitaxial La0.67Ca0.33MnO3:SrTiO3 (LCMO:STO) composite thin films have been grown on single crystal LaAlO3(001) substrates by a cost effective polymer-assisted deposition method. Both x-ray diffraction and high-resolution transmission electron microscopy confirm the growth of epitaxial films with an epitaxial relationship between the films and the substrates as (002)film||(002)sub and [202]film||[202]sub. The transport property measurement shows that the STO phase significantly increases the resistivity and enhances the magnetoresistance (MR) effect of LCMO and moves the metal-insulator transition to lower temperatures. For example, the MR values measured at magnetic fields of 0 and 3 T are −44.6% at 255 K for LCMO, −94.2% at 125 K for LCMO:3% STO, and −99.4% at 100 K for LCMO:5% STO, respectively.
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