Electrochemical Capacitance of CO-Terminated Pt(111) Dominated by the CO-Solvent Gap.
Electrochemical Capacitance of CO-Terminated Pt(111) Dominated by the CO-Solvent Gap.
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DOI：
10.1021/acs.jpclett.7b02383
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发表时间：
2017-11-02
期刊：
影响因子：
--
通讯作者：
Schwarz KA
中科院分区：
文献类型：
--
作者：
Sundararaman R;Figueiredo MC;Koper MTM;Schwarz KA
电化学双层内的电场分布以复杂的方式取决于电极和电解质。这些领域强烈影响电极-电解质界面的化学动力学，但不能直接测量亚分子分辨率。我们报道了CO封端的Pt（111）水界面的电容测量实验。通过比较这些测量与第一性原理密度泛函理论（DFT）计算，我们推断微观场分布和分解的贡献，从各个空间区域的接口的逆电容。我们发现，CO是强烈的电子耦合到Pt，和大部分的界面电位差出现在两端之间的差距终止O和水，而不是整个CO分子如先前假设的。这种“间隙电容”导致疏水终止降低了水相Pt-CO界面的总电容，并使其对电解质浓度不太敏感相比，裸金属。
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.
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