The distribution of electric fields within the electrochemical double layer depends on both the electrode and electrolyte in complex ways. These fields strongly influence chemical dynamics in the electrode-electrolyte interface, but cannot be measured directly with sub-molecular resolution. We report experimental capacitance measurements for aqueous interfaces of CO-terminated Pt(111). By comparing these measurements with first-principles density-functional theory (DFT) calculations, we infer microscopic field distributions and decompose contributions to the inverse capacitance from various spatial regions of the interface. We find that the CO is strongly electronically coupled to the Pt, and that most of the interfacial potential difference appears across the gap between the terminating O and water, and not across the CO molecule as previously hypothesized. This `gap capacitance' resulting from hydrophobic termination lowers the overall capacitance of the aqueous Pt-CO interface, and makes it less sensitive to electrolyte concentration compared to the bare metal.
Confinement-controlled Water Engenders High Energy Density Electrochemical-double-layer Capacitance
Skolkovo Institute of Science and Technology（斯克隆沃科学技术研究所）；Karlsruhe Institute of Technology（卡尔斯鲁厄理工学院）；École Polytechnique Fédérale de Lausanne (EPFL)（洛桑联邦理工学院）；Max Planck Institute for Polymer Research（马克斯·普朗克高分子研究所）
Pilot study of electrochemical reduction of selected nucleotides and double-stranded DNA at pristine micro-/ultrananocrystalline boron-doped diamond electrodes at very negative potentials
A Theoretical Investigation of the Grand- and the Canonical Potential Energy Surface: The Interplay between Electronic and Geometric Response at Electrified Interfaces
Ion Transport in an Electrochemical Cell: A Theoretical Framework to Couple Dynamics of Double Layers and Redox Reactions for Multicomponent Electrolyte Solutions
Unveiling the Influence of Graphitic Nanocarbon Structures, Defects, and Surface Functional Groups on Supercapacitive Performance in LiTFSI Electrolyte
Sirindhorn International Institute of Technology, Thammasat University（诗琳通国际理工学院，坦布拉大学）；Université de Haute-Alsace, Institut de Science des Matériaux de Mulhouse (IS2M), CNRS UMR 7361（上阿尔萨斯大学，米卢斯材料科学研究所 (IS2M)，法国国家科学研究中心 UMR 7361）；Université de Strasbourg（斯特拉斯堡大学）；Réseau sur le Stockage Electrochimique de l’Energie (RS2E), CNRS FR3459（电化学储能网络 (RS2E)，法国国家科学研究中心 FR3459）；International Research and Education Center for Element Science, Faculty of Science and Technology, Gunma University（群马大学理学院元素科学国际研究与教育中心）；Division of Chemical Engineering, Faculty of Engineering, Rajamangala University of Technology Krungthep（曼谷皇家理工大学工程学院化学工程系）
