Tailoring the Acidity of Liquid Media with Ionizing Radiation: Rethinking the Acid–Base Correlation beyond pH

Fritsch, Birk; Körner, Andreas; Couasnon, Thaïs; Blukis, Roberts; Taherkhani, Mehran; Benning, Liane G.; Jank, Michael P. M.; Spiecker, Erdmann; Hutzler, Andreas

doi:10.1021/acs.jpclett.3c00593

Cited by 25 publications

(20 citation statements)

References 52 publications

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“…At dose rates relevant to LP-TEM, those are formed within a fraction of a second. 10,32 Note, however, that the transient period can extend up to several hours at low dose rates. 20,32 To reduce the parameter landscape within radiation chemistry simulations in LP-TEM, first the basis of all aqueous solutions is considered.…”

Section: Resultsmentioning

confidence: 99%

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Precision of Radiation Chemistry Networks: Playing Jenga with Kinetic Models for Liquid-Phase Electron Microscopy

Fritsch,

Malgaretti,

Harting

et al. 2023

Precision Chemistry

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Liquid-phase transmission electron microscopy (LP-TEM) is a powerful tool to gain unique insights into dynamics at the nanoscale. The electron probe, however, can induce significant beam effects that often alter observed phenomena such as radiolysis of the aqueous phase. The magnitude of beam-induced radiolysis can be assessed by means of radiation chemistry simulations potentially enabling quantitative application of LP-TEM. Unfortunately, the computational cost of these simulations scales with the amount of reactants regarded. To minimize the computational cost, while maintaining accurate predictions, we optimize the parameter space for the solution chemistry of aqueous systems in general and for diluted HAuCl 4 solutions in particular. Our results indicate that sparsened kinetic models can accurately describe steady-state formation during LP-TEM and provide a handy prerequisite for efficient multidimensional modeling. We emphasize that the demonstrated workflow can be easily generalized to any kinetic model involving multiple reaction pathways.

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Section: Resultsmentioning

confidence: 99%

“…10,32 Note, however, that the transient period can extend up to several hours at low dose rates. 20,32 To reduce the parameter landscape within radiation chemistry simulations in LP-TEM, first the basis of all aqueous solutions is considered. By taking a comprehensive reaction set, we start with 17 reactants, namely…”

Section: Resultsmentioning

confidence: 99%

Precision of Radiation Chemistry Networks: Playing Jenga with Kinetic Models for Liquid-Phase Electron Microscopy

Fritsch,

Malgaretti,

Harting

et al. 2023

Precision Chemistry

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show abstract

“…The simulations predict the most prevalent radiolytic products to be H 2 and H 2 O 2 , followed by OH • and O 2 , short lived hydrated electrons, e – (aq), and atomic H. They also predicted a drop in pH for irradiated neutral solutions to pH 5 at 10 7 Gy/s, which recently has been considered as an decrease in both pH and pOH . Predictions as those made by Schneider et al currently form the foundation for interpreting the many varied radiolytic effects influencing LPEM results in SEM and TEM at a given dose rate, given the lack of other direct approaches to assess radiolytic products with the limited analytical capabilities in current LPEM systems …”

Section: Introductionmentioning

confidence: 84%

Quantifying Aqueous Radiolytic Products in Liquid Phase Electron Microscopy

et al. 2023

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Liquid phase electron microscopy (LPEM) is rapidly gaining importance for in situ studies of chemical processes. However, radiolysis due to interactions between the liquid medium and the electron beam results in the formation of highly reactive species that influence the studied processes. Our understanding of LPEM radiolysis is currently based on simulations that rely on data collected from measurements at low electron flux intensities, requiring extrapolation by several orders of magnitude to match the intensities utilized in LPEM. We demonstrate direct electrochemical measurements of radiolytic products during in situ LPEM, which allows us to directly assess the high flux accuracy of low-flux radiolysis models. Using a specially designed liquid cell for electrochemical detection, we quantify the primary expected stable radiolysis products H 2 and H 2 O 2 in a scanning electron microscope. We find H 2 production is rapid and in reasonable agreement with predictions, but H 2 O 2 levels are lower than expected from the low-flux extrapolated radiolysis models. This study demonstrates a new approach to experimentally validate simulations and indicates that the chemical environment may be far more reducing than predicted from current models.

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“…As such, the radiolytic acidity 𝜋* alongside with the radiolytic ion product K w * was introduced. Those relate to both, [H + ] and [OH − ] under exposure to ionizing radiation: [57] 𝜋 * = lg…”

Section: Model Comparisonmentioning

confidence: 99%

Goethite Mineral Dissolution to Probe the Chemistry of Radiolytic Water in Liquid‐Phase Transmission Electron Microscopy

et al. 2023

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Liquid‐Phase Transmission Electron Microscopy (LP‐TEM) enables in situ observations of the dynamic behavior of materials in liquids at high spatial and temporal resolution. During LP‐TEM, incident electrons decompose water molecules into highly reactive species. Consequently, the chemistry of the irradiated aqueous solution is strongly altered, impacting the reactions to be observed. However, the short lifetime of these reactive species prevent their direct study. Here, the morphological changes of goethite during its dissolution are used as a marker system to evaluate the influence of radiation on the changes in solution chemistry. At low electron flux density, the morphological changes are equivalent to those observed under bulk acidic conditions, but the rate of dissolution is higher. On the contrary, at higher electron fluxes, the morphological evolution does not correspond to a unique acidic dissolution process. Combined with kinetic simulations of the steady state concentrations of generated reactive species in the aqueous medium, the results provide a unique insight into the redox and acidity interplay during radiation induced chemical changes in LP‐TEM. The results not only reveal beam‐induced radiation chemistry via a nanoparticle indicator, but also open up new perspectives in the study of the dissolution process in industrial or natural settings.

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Tailoring the Acidity of Liquid Media with Ionizing Radiation: Rethinking the Acid–Base Correlation beyond pH

Cited by 25 publications

References 52 publications

Precision of Radiation Chemistry Networks: Playing Jenga with Kinetic Models for Liquid-Phase Electron Microscopy

Precision of Radiation Chemistry Networks: Playing Jenga with Kinetic Models for Liquid-Phase Electron Microscopy

Quantifying Aqueous Radiolytic Products in Liquid Phase Electron Microscopy

Goethite Mineral Dissolution to Probe the Chemistry of Radiolytic Water in Liquid‐Phase Transmission Electron Microscopy

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