Issue 38, 2019

Controlling the radical-induced redox chemistry inside a liquid-cell TEM


With Liquid-Cell Transmission Electron Microscopy (LCTEM) we can observe the kinetic processes taking place in nanoscale materials that are in a solvated environment. However, the beam-driven solvent radiolysis, which results from the microscope's high-energy electron beam, can dramatically influence the dynamics of the system. Recent research suggests that radical-induced redox chemistry can be used to investigate the various redox-driven dynamics for a wide range of functional nanomaterials. In view of this, the interplay between the formation of various highly reactive radiolysis species and the nanomaterials under investigation needs to be quantified in order to formulate new strategies for nanomaterials research. We have developed a comprehensive radiolysis model by using the electron-dose rate, the temperature of the solvent, the H2 and O2 gas saturation concentrations and the pH values as the key variables. These improved kinetic models make it possible to simulate the material's specific radical-induced redox reactions. As in the case of the Au model system, the kinetic models are presented using Temperature/Dose-rate Redox potential (TDR) diagrams, which indicate the equilibrium [Au0]/[Au+] concentration ratios that are directly related to the temperature-/dose-rate-dependent precipitation or dissolution regions of the Au nanoparticles. Our radiolysis and radical-induced redox models were successfully verified using previously reported data from low-dose experiments with γ radiation and experimentally via TDR-dependent LCTEM. The presented study represents a holistic approach to the radical-induced redox chemistry in LCTEM, including the complex kinetics of the radiolysis species and their influence on the redox chemistry of the materials under investigation, which are represented here by Au nanoparticles.

Graphical abstract: Controlling the radical-induced redox chemistry inside a liquid-cell TEM

Supplementary files

Article information

Article type
Edge Article
07 May 2019
14 Aug 2019
First published
16 Aug 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 8735-8743

Controlling the radical-induced redox chemistry inside a liquid-cell TEM

B. Ambrožič, A. Prašnikar, N. Hodnik, N. Kostevšek, B. Likozar, K. Ž. Rožman and S. Šturm, Chem. Sci., 2019, 10, 8735 DOI: 10.1039/C9SC02227A

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