期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2016
卷号：113
期号：47
页码：13324-13329
DOI：10.1073/pnas.1608730113
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：SignificanceIn situ characterization of kinetics at electrode-electrolyte interfaces (EEIs) is crucial to the rational design of efficient and sustainable solid-state electrochemical technologies. A significant advancement has been made to rationally understand processes at EEIs using solid-state in situ thin-film electrochemical cells fabricated using specially designed ionic liquid membranes with excellent mass-transfer properties. The in situ cells are used to characterize well-defined EEIs generated using ion soft-landing (SL) in controlled environments, both in vacuum and in the presence of reactant gases. Populating EEIs with precisely defined electroactive species using SL facilitates molecular-level understanding of electron transfer processes within deposited species and between species and electrodes, thus providing a powerful methodology to characterize technologically relevant EEIs during operation. Molecular-level understanding of electrochemical processes occurring at electrode-electrolyte interfaces (EEIs) is key to the rational development of high-performance and sustainable electrochemical technologies. This article reports the development and application of solid-state in situ thin-film electrochemical cells to explore redox and catalytic processes occurring at well-defined EEIs generated using soft-landing (SL) of mass- and charge-selected cluster ions. In situ cells 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, demonstrated to be a unique tool for studying fundamental processes occurring at EEIs. Using an aprotic cell, the effect of charge state ([IMG]f1.gif" ALT="Formula" BORDER="0">) and the contribution of building blocks of Keggin polyoxometalate (POM) clusters to redox processes are characterized by populating EEIs with POM anions generated by electrospray ionization and gas-phase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt30 [~]1 nm diameter), thus demonstrating the capability of the cell for probing catalytic reactions in controlled gaseous environments. By combining the developed in situ electrochemical cell with ion SL we established a versatile method to characterize the EEI in solid-state redox systems and reactive electrochemistry at precisely defined conditions. This capability will advance the molecular-level understanding of processes occurring at EEIs that are critical to many energy-related technologies.
