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Mechanism for plasmon-generated solvated electrons.

ABSTRACT: Solvated electrons are powerful reducing agents capable of driving some of the most energetically expensive reduction reactions. Their generation under mild and sustainable conditions remains challenging though. Using near-ultraviolet irradiation under low-intensity one-photon conditions coupled with electrochemical and optical detection, we show that the yield of solvated electrons in water is increased more than 10 times for nanoparticle-decorated electrodes compared to smooth silver electrodes. Based on the simulations of electric fields and hot carrier distributions, we determine that hot electrons generated by plasmons are injected into water to form solvated electrons. Both yield enhancement and hot carrier production spectrally follow the plasmonic near-field. The ability to enhance solvated electron yields in a controlled manner by tailoring nanoparticle plasmons opens up a promising strategy for exploiting solvated electrons in chemical reactions.

SUBMITTER: Al-Zubeidi A

PROVIDER: S-EPMC9934022 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

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Mechanism for plasmon-generated solvated electrons.

Al-Zubeidi Alexander A Ostovar Behnaz B Carlin Claire C CC Li Boxi Cam BC Lee Stephen A SA Chiang Wei-Yi WY Gross Niklas N Dutta Sukanya S Misiura Anastasiia A Searles Emily K EK Chakraborty Amrita A Roberts Sean T ST Dionne Jennifer A JA Rossky Peter J PJ Landes Christy F CF Link Stephan S

Proceedings of the National Academy of Sciences of the United States of America 20230110 3

Solvated electrons are powerful reducing agents capable of driving some of the most energetically expensive reduction reactions. Their generation under mild and sustainable conditions remains challenging though. Using near-ultraviolet irradiation under low-intensity one-photon conditions coupled with electrochemical and optical detection, we show that the yield of solvated electrons in water is increased more than 10 times for nanoparticle-decorated electrodes compared to smooth silver electrode ...[more]

PMID: 36626548

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Project description:We investigated excess electron solvation dynamics in (NH3)n- ammonia clusters in the n = 8-32 size range by performing finite temperature molecular dynamics simulations. In particular, we focused on three possible scenarios. The first case is designed to model electron attachment to small neutral ammonia clusters (n ≤ ∼10) that form hydrogen-bonded chains. The excess electron is bound to the clusters via dipole bound states, and persists with a VDE of ∼160 meV at 100 K for the n = 8 cluster. The coupled nuclear and electronic relaxation is fast (within ∼100 fs) and takes place predominantly by intermolecular librational motions and the intramolecular umbrella mode. The second scenario illustrates the mechanism of excess electron attachment to cold compact neutral clusters of medium size (8 ≤ n ≤ 32). The neutral clusters show increasing tendency with size to bind the excess electron on the surface of the clusters in weakly bound, diffuse, and highly delocalized states. Anionic relaxation trajectories launched from these initial states provide no indication for excess electron stabilization for sizes n < 24. Excess electrons are likely to autodetach from these clusters. The two largest investigated clusters (n = 24 and 32) can accommodate the excess electron in electronic states that are mainly localized on the surface, but they may be partly embedded in the cluster. In the last 500 fs of the simulated trajectories, the VDE of the solvated electron fluctuates around ∼200 meV for n = 24 and ∼500 meV for n = 32, consistent with the values extrapolated from the experimentally observed linear VDE-n-1/3 trend. In the third case, we prepared neutral ammonia cluster configurations, including an n = 48 cluster, that contain possible electron localization sites within the interior of the cluster. Excess electrons added to these clusters localize in cavities with high VDEs up to 1.9 eV for n = 48. The computed VDE values for larger clusters are considerably higher than the experimentally observed photoelectric threshold energy for the solvated electron in bulk ammonia (∼1.4 eV). Molecular dynamics simulations launched from these initial cavity states strongly indicate, however, that these cavity structures exist only for ∼200 fs. During the relaxation the electron leaves the cavity and becomes delocalized, while the cluster loses its initial compactness.

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Mechanism for plasmon-generated solvated electrons.

Publications

Mechanism for plasmon-generated solvated electrons.

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