In situ solid-state electrochemistry of mass-selected ions at well-defined electrode-electrolyte interfaces
In situ solid-state electrochemistry of mass-selected ions at well-defined electrode-electrolyte interfaces
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DOI：
10.1073/pnas.1608730113
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发表时间：
2016-11-22
影响因子：
11.1
通讯作者：
Laskin, Julia
中科院分区：
文献类型：
--
作者：
Prabhakaran, Venkateshkumar;Johnson, Grant E.;Laskin, Julia
对电极-电解质界面（EEI）发生的电化学过程的分子水平理解是合理开发高性能和可持续电化学技术的关键。本文报道了固态原位薄膜电化学电池的开发和应用，以探索使用质量和电荷选择的簇离子的软着陆 (SL) 生成的明确 EEI 中发生的氧化还原和催化过程。使用精心设计的纳米多孔离子液体膜制造具有优异传质特性的原位电池。 SL 能够将其他技术无法获得的纯活性物质沉积到电极表面，并精确控制电荷状态、成分和动能。因此，SL 被证明是研究 EEI 中发生的基本过程的独特工具。使用非质子电池，通过用电喷雾电离和气相解离产生的 POM 阴离子填充 EEI 来表征电荷态 (PMo12O403-/2-) 的影响以及 Keggin 多金属氧酸盐 (POM) 簇结构单元对氧化还原过程的贡献。此外，还开发了一种质子传导电池来表征裸 Pt 簇（Pt-30 直径类似于 1 nm）的氧还原活性，从而证明了该电池在受控气体环境中探测催化反应的能力。通过将开发的原位电化学电池与 ion SL 相结合，我们建立了一种通用方法，可以在精确定义的条件下表征固态氧化还原系统和反应电化学中的 EEI。这种能力将促进对 EEI 发生的过程的分子水平理解，这对许多能源相关技术至关重要。
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 (PMo12O403-/2-) 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 gasphase dissociation. Additionally, a proton-conducting cell has been developed to characterize the oxygen reduction activity of bare Pt clusters (Pt-30 similar to 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.