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Size dependence of hydrophobic hydration at electrified gold/water interfaces [Chemistry]
Proceedings of the National Academy of Sciences of the United States of America ( IF 9.412 ) Pub Date : 2021-04-13 , DOI: 10.1073/pnas.2023867118
Alessandra Serva, Mathieu Salanne, Martina Havenith, Simone Pezzotti

Hydrophobic hydration at metal/water interfaces actively contributes to the energetics of electrochemical reactions, e.g. CO2 and N2 reduction, where small hydrophobic molecules are involved. In this work, constant applied potential molecular dynamics is employed to study hydrophobic hydration at a gold/water interface. We propose an adaptation of the Lum–Chandler–Weeks (LCW) theory to describe the free energy of hydrophobic hydration at the interface as a function of solute size and applied voltage. Based on this model we are able to predict the free energy cost of cavity formation at the interface directly from the free energy cost in the bulk plus an interface-dependent correction term. The interfacial water network contributes significantly to the free energy, yielding a preference for outer-sphere adsorption at the gold surface for ideal hydrophobes. We predict an accumulation of small hydrophobic solutes of sizes comparable to CO or N2, while the free energy cost to hydrate larger hydrophobes, above 2.5-Å radius, is shown to be greater at the interface than in the bulk. Interestingly, the transition from the volume dominated to the surface dominated regimes predicted by the LCW theory in the bulk is also found to take place for hydrophobes at the Au/water interface but occurs at smaller cavity radii. By applying the adapted LCW theory to a simple model addition reaction, we illustrate some implications of our findings for electrochemical reactions.



中文翻译:

电气化金/水界面上疏水水合的尺寸依赖性[化学]

金属/水界面的疏水水合积极地促进了电化学反应的能量,例如 CØ2个ñ2个减少,其中涉及小的疏水分子。在这项工作中,采用恒定的潜在分子动力学来研究金/水界面的疏水水合。我们提议采用Lum–Chandler–Weeks(LCW)理论,以描述界面上疏水水合的自由能与溶质大小和施加电压的关系。基于此模型,我们能够直接根据本体中的自由能成本加上依赖于界面的校正项来预测界面处空腔形成的自由能成本。界面水网络极大地促进了自由能,因此对于理想的疏水物而言,金表面的外球吸附更为可取。我们预测了可与CO或ñ2个,而在半径大于2.5-Å的范围内水合较大的疏水物的自由能成本则显示出比在主体中大。有趣的是,对于LC / Ab /水界面上的疏水物,也发生了由LCW理论预测的从体积主导到表面主导的转变,但发生在空腔半径较小的地方。通过将适用的LCW理论应用于简单的模型加成反应,我们说明了我们的发现对于电化学反应的某些含义。

更新日期:2021-04-06
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