Determination of Redox Reaction Rates and Orders by In Situ Liquid Cell Electron Microscopy of Pd and Au Solution Growth.

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Bibliographic Details
Title: Determination of Redox Reaction Rates and Orders by In Situ Liquid Cell Electron Microscopy of Pd and Au Solution Growth.
Authors: Sutter, Eli A.1 esutter@bnl.gov, Sutter, Peter W.1
Source: Journal of the American Chemical Society. 12/3/2014, Vol. 136 Issue 48, p16865-16870. 6p.
Subjects: Oxidation-reduction reaction, Scanning transmission electron microscopy, Nanoparticles, Lead compounds, Electron beam research
Abstract: In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important, as they provide direct insight into processes in liquids, such as solution growth of nanoparticles, among others. In liquid cell TEM/STEM redox reaction experiments, the hydrated electrons e-aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e-aq generated by the electron beam during in situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e-aq]. By comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e-aq] but also the rate of reduction of a metal-ion complex to zerovalent metal atoms in solution. [ABSTRACT FROM AUTHOR]
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Database: Engineering Source
Description
Abstract:In-situ liquid cell transmission and scanning transmission electron microscopy (TEM/STEM) experiments are important, as they provide direct insight into processes in liquids, such as solution growth of nanoparticles, among others. In liquid cell TEM/STEM redox reaction experiments, the hydrated electrons e-aq created by the electron beam are responsible for the reduction of metal-ion complexes. Here we investigate the rate equation of redox reactions involving reduction by e-aq generated by the electron beam during in situ liquid TEM/STEM. Specifically we consider the growth of Pd on Au seeds in aqueous solutions containing Pd-chloro complexes. From the quantification of the rate of Pd deposition at different electron beam currents and as a function of distance from a stationary, nanometer-sized exciting beam, we determine that the reaction is first order with respect to the concentration of hydrated electrons, [e-aq]. By comparing Pd- and Au-deposition, we further demonstrate that measurements of the local deposition rate on nanoparticles in the solution via real-time imaging can be used to measure not only [e-aq] but also the rate of reduction of a metal-ion complex to zerovalent metal atoms in solution. [ABSTRACT FROM AUTHOR]
ISSN:00027863
DOI:10.1021/ja508279v