Fabrication of High‐aspect Ratio (HAR) Palladium Nanorod‐modified Electrodes for Raman Spectroelectrochemical Studies of Thiolate Desorption from HAR Nanomaterials |
| |
| Authors: | Michael B Pomfret Jeremy J Pietron |
| |
| Affiliation: | 1. Code 6110, Chemical Dynamics and Diagnostics Branch;2. Lab/Cor Materials, LLC., Seattle;3. Code 6170, Surface Chemistry Branch, Naval Research Laboratory, Washington |
| |
| Abstract: | We describe a method to fabricate electrodes modified with high‐aspect ratio (HAR) palladium (Pd) nanorods derived from the electrochemical reduction of Pd salts in polycarbonate track‐etched membranes. The HAR Pd nanorod‐modified electrode platform enables direct spectroscopic observation of electrochemical processes particular to HAR forms of nano‐Pd using Raman spectroelectrochemistry. In the present study, we use this platform to observe an anomalous mechanism of oxidative electrochemical desorption of the probe molecule benzenethiol (BT) from the HAR Pd surface. At HAR Pd, the Pd?S bond between the Pd nanorods and BT severs upon oxidation of the Pd surface, whereas on the surface of spherical nano‐Pd, the C?S bond in BT is broken, as is more typically observed for sulfur‐containing organic molecules adsorbed to Pd surfaces. Using this probe reaction, we demonstrate the suitability of this HAR nanorod‐modified electrode platform for the investigation of anomalous electrochemical phenomena observed at HAR Pd for reactions that involve adsorbed intermediates in general – including not only adsorbed sulfur – but in principle also for the electrochemical oxidation of alternative fuels such as ethanol and methanol. |
| |
| Keywords: | electrocatalysis high-aspect ratio nanorods Raman spectroscopy spectroelectrochemistry sulfur-tolerant |
|
|
