Title: In situ solid-state electrochemistry of mass-selected ions at well-defined electrode–electrolyte interfaces

Abstract

Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEI) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and first application of solid-state in situ electrochemical probes to study redox and catalytic processes occurring at well-defined EEI generated using soft-landing of mass- and charge-selected cluster ions (SL). In situ electrochemical probes with excellent mass transfer properties are fabricated using carefully-designed nanoporous ionic liquid membranes. SL enables deposition of pure active species that are not obtainable with other techniques onto electrode surfaces with precise control over charge state, composition, and kinetic energy. SL is, therefore, a unique tool for studying fundamental processes occurring at EEI. For the first time using an aprotic electrochemical probe, the effect of charge state (PMo₁₂O₄₀^3-/2-) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEI with novel POM anions generated by electrospray ionization and gas phase dissociation. Additionally, a proton conducting electrochemical probe has been developed to characterize the reactive electrochemistry (oxygen reduction activity) of bare Pt clusters (Pt₄₀ ~1 nm diameter), thus demonstrating the capability of the probe for studying reactions in controlled gaseous environments. The newlymore » developed in situ electrochemical probes combined with ion SL provide a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely-defined conditions. Furthermore, this capability will advance molecular-level understanding of processes occurring at EEI that are critical to many energy-related technologies.« less

Authors:

Prabhakaran, Venkateshkumar  ^[1];

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• Search DOE PAGES for ORCID "0000-0001-6692-6488"

Johnson, Grant E. ^[1]; Wang, Bingbing ^[2]; Laskin, Julia ^[1]

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+ Show Author Affiliations

1. Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA 99352,
2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA 99352

Publication Date:

Mon Nov 07 00:00:00 EST 2016

Research Org.:

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Org.:

USDOE

OSTI Identifier:

1331219

Alternate Identifier(s):

OSTI ID: 1339859

Report Number(s):

PNNL-SA-118405
Journal ID: ISSN 0027-8424

Grant/Contract Number:  

KC030202047327; AC05-76RL01830

Resource Type:

Published Article

Journal Name:

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

Additional Journal Information:

Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 47; Journal ID: ISSN 0027-8424

Publisher:

Proceedings of the National Academy of Sciences

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; In situ electrochemistry; electrode-electrolyte interface; ion soft-landing; ionic liquid membrane; clusters; Environmental Molecular Sciences Laboratory