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

Abstract

A holistically described radical-induced redox chemistry modelling allows for a direct assessment of the in situ experiments inside a liquid-cell TEM.

Abstract

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 H ₂ and O ₂ 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 [Au ⁰]/[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.

Notes

†Electronic supplementary information (ESI) available: General model description of the water radiolysis, reaction rates and G-values. Estimation of the reaction-rate constants of the water radiolysis products with gold species. Sensitivity analysis of the temperature-dependent part of the H ₂ and O ₂ solubility. Model details for the verification by low-dose experiments using γ radiation. Ex situ SAED analysis of the conformation of gold NPs. See DOI: 10.1039/c9sc02227a