Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO$^−_2$ as a plasma-derived reducing agent

Srivastava, Tanubhav; Chaudhuri, Subhajyoti; Rich, Christopher C.; Schatz, George C.; Frontiera, Renee R.; Bruggeman, Peter

doi:10.1063/5.0190348

Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO$$^−_2$$ as a plasma-derived reducing agent

Journal Article · Mon Mar 04 00:00:00 EST 2024 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0190348· OSTI ID:3024918

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Univ. of Minnesota, Minneapolis, MN (United States)
Northwestern Univ., Evanston, IL (United States)

Many applications involving plasma–liquid interactions depend on the reactive processes occurring at the plasma–liquid interface. In this article, we report on a falling liquid film plasma reactor allowing for in situ optical absorption measurements of the time-dependence of the ferricyanide/ferrocyanide redox reactivity, complemented with ex situ measurement of the decomposition of formate. We found excellent agreement between the measured decomposition percentages and the diffusion-limited decomposition of formate by interfacial plasma-enabled reactions, except at high pH in thin liquid films, indicating the involvement of previously unexplored plasma-induced liquid phase chemistry enabled by long-lived reactive species. We also determined that high pH facilitates a reduction-favoring environment in ferricyanide/ferrocyanide redox solutions. In situ conversion measurements of a 1:1 ferricyanide/ferrocyanide redox mixture exceed the measured ex situ conversion and show that conversion of a 1:1 ferricyanide/ferrocyanide mixture is strongly dependent on film thickness. We identified three dominant processes: reduction faster than ms time scales for film thicknesses >100 µm, •OH-driven oxidation on time scales of <10 ms, and reduction on 15 ms time scales for film thickness <100 µm. We attribute the slow reduction and larger formate decomposition at high pH to HO$$^−_2$$ formed from plasma-produced H₂O₂ enabled by the high pH at the plasma–liquid interface as confirmed experimentally and by computed reaction rates of HO$$^−_2$$ with ferricyanide. Overall, this work demonstrates the utility of liquid film reactors in enabling the discovery of new plasma-interfacial chemistry and the utility of atmospheric plasmas for electrodeless electrochemistry.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Michigan, Ann Arbor, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE Office of Science (SC), Fusion Energy Sciences (FES)

Grant/Contract Number:: SC0020232

Other Award/Contract Number:: W911NF-20-1-0105

OSTI ID:: 3024918

Alternate ID(s):: OSTI ID: 2578482

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 160; ISSN 1089-7690; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO$$^−_2$$ as a plasma-derived reducing agent

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