Nanosecond Pulse Radiolysis of Nanoconfined Water

Musat, Raluca; Cook, Andrew R.; Renault, Jean Philippe; Crowell, Robert A.

doi:10.1021/jp301000c

Cited by 24 publications

(22 citation statements)

References 72 publications

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“…Furthermore, these authors were only able to determine that the hydrated electrons resided <1 nm from the interface. Because 1 nm is roughly three water molecular diameters, this means that the SHG experiment could effectively be probing hydrated electrons in the bulk. − It is also worth noting that pulse-radiolysis experiments that produced hydrated electrons in water that was confined in 1 nm diameter silica pore glasses found that the confined electrons retain their bulk absorption spectrum, consistent with the idea that electrons need to be closer than 0.5 nm to a surface if non-bulk-like interfacial properties are to be detected …”

mentioning

confidence: 77%

Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface

Casey

Schwartz

Glover

2016

J. Phys. Chem. Lett.

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The properties of the hydrated electron at the air/water interface are computed for both a cavity and a noncavity model using mixed quantum/classical molecular dynamics simulation. We take advantage of our recently developed formalism for umbrella sampling with a restrained quantum expectation value to calculate free-energy profiles of the hydrated electron's position relative to the water surface. We show that it is critical to use an instantaneous description of the air/water interface rather than the Gibbs' dividing surface to obtain accurate potentials of mean force. We find that noncavity electrons, which prefer to encompass several water molecules, avoid the interface where water molecules are scarce. In contrast, cavity models of the hydrated electron, which prefer to expel water, have a local free-energy minimum near the interface. When the cavity electron occupies this minimum, its absorption spectrum is quite red-shifted, its binding energy is significantly lowered, and its dynamics speed up quite a bit compared with the bulk, features that have not been found by experiment. The surface activity of the electron therefore serves as a useful test of cavity versus noncavity electron solvation.

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mentioning

confidence: 77%

Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface

Casey

Schwartz

Glover

2016

J. Phys. Chem. Lett.

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“…The reaction proceeds so efficiently that the radiolysis can be conducted at room temperature and ambient pressure. 29 Essentially, the species of and with low redox potentials - * serve as in-situ reductants, while the oxidative radical is scavenged by common alcohol additives, such as isopropanol and ethanol. Starting from this principle, Zhao and co-workers reported the synthesis of monodispersed Ag nanoparticles (NPs)/graphene nanocomposites using gamma radiation.…”

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confidence: 99%

Photon-induced synthesis of ultrafine metal nanoparticles on graphene as electrocatalysts: impact of functionalization and doping

et al. 2020

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“…This has been associated with an unobservable H + H reaction in talc 36 . Furthermore, pulse radiolysis experiments performed in nanoporous silica have attributed most of the decay of solvated electron in the ns-µs timescale range to the e − + SiOH → SiO − + H reaction 74 . This suggests that the reaction with Mu, which is happening in the same timescale, occurs with H atoms and not with electrons, as electrons will react preferentially with MgOH groups in the present case.…”

Section: Resultsmentioning

confidence: 99%

Influence of confinement on free radical chemistry in layered nanostructures

Ghandi

Landry

et al. 2019

Sci Rep

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The purpose of the present work was to study how chemical reactions and the electronic structure of atoms are affected by confinement at the sub-nanometer scale. To reach this goal, we studied the H atom in talc, a layered clay mineral. Talc is a highly 2D-confining material with the width of its interlayer space close to angstrom. We investigated talc with a particle accelerator-based spectroscopic method that uses elementary particles. This technique generates an exotic atom, muonium (Mu), which can be considered as an isotope of the H atom. Moreover, the technique allows us to probe a single atom (H atom) at any time and explore the effects of the layered clay on a single ion (proton) or atom. The cation/electron recombination happens in two time windows: one faster than a nanosecond and the other one at longer than microseconds. This result suggests that two types of electron transfer processes take place in these clay minerals. Calculations demonstrated that the interlayer space acts as a catalytic surface and is the primary location of cation/electron recombination in talc. Moreover, the studies of the temperature dependence of Mu decay rates, due to the formation of the surrogate of H2, is suggestive of an “H2” formation reaction that is thermally activated above 25 K, but governed by quantum diffusion below 25 K. The experimental and computational studies of the hyperfine coupling constant of Mu suggest that it is formed in the interlayer space of talc and that its electronic structure is extremely changed due to confinement. All these results imply that the chemistry could be strongly affected by confinement in the interlayer space of clays.

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Nanosecond Pulse Radiolysis of Nanoconfined Water

Cited by 24 publications

References 72 publications

Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface

Free Energies of Cavity and Noncavity Hydrated Electrons Near the Instantaneous Air/Water Interface

Photon-induced synthesis of ultrafine metal nanoparticles on graphene as electrocatalysts: impact of functionalization and doping

Influence of confinement on free radical chemistry in layered nanostructures

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