Hydrogen-Induced Restructuring of a Cu(100) Electrode in Electroreduction Conditions
Hydrogen-Induced Restructuring of a Cu(100) Electrode in Electroreduction Conditions
复制标题
电还原条件下 Cu(100) 电极的氢致重构
DOI：
10.1021/jacs.2c06188
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发表时间：
2022
影响因子：
15
通讯作者：
Alexandrova, Anastassia N.
中科院分区：
文献类型：
--
作者：
Zhang, Zisheng;Wei, Ziyang;Sautet, Philippe;Alexandrova, Anastassia N.
在电化学条件下的Cu表面的重排是已知的主要电催化反应的表面活化中发挥关键作用。尽管从表面敏感光谱和显微镜对这种重排有广泛的实验见解，但这些方法的空间和时间分辨率不足以提供电化学界面的原子图像。理论表征也受到挑战的多样性重组配置，表面化学计量，吸附配置，和电极电位的影响。在这里，原子的洞察力的电化学界面的重组是从第一原理。采用巨正则密度泛函理论和全局优化方法，结合从头算分子动力学和机理计算，研究了不同外加电位和吸附质覆盖率下Cu（100）的结构重构.我们表明，电还原条件导致形成的移位行重建Cu（100），诱导氢吸附。当Cu-H键合充分削弱顶部和子层之间的Cu-Cu键时，在1/6 ML H覆盖度处开始重建，并且当H吸附物填充所有产生的3重中空位点时，在1/3 ML处进一步稳定重建。模拟的重构界面的扫描隧道显微镜（STM）图像与实验situSTM一致。然而，与热力学预测相比，实验中的重构事件的起始发生在更负的施加电压下。这是由于动力学效应的重组，我们描述通过不同的统计模型，以产生潜在的和pH值依赖的表面稳定性图。这份手稿提供了丰富的原子洞察表面重组在电还原条件下，这是需要的理解和设计的铜基材料的电催化过程。它也提供了方法学研究问题的原位电极重建。
The rearrangement of Cu surfaces under electrochemical conditions is known to play a key role in the surface activation for major electrocatalytic reactions. Despite the extensive experimental insights into such rearrangements, from surface-sensitive spectroscopy and microscopy, the spatial and temporal resolution of these methods is insufficient to provide an atomistic picture of the electrochemical interface. Theoretical characterization has also been challenged by the diversity of restructuring configurations, surface stoichiometry, adsorbate configurations, and the effect of the electrode potential. Here, atomistic insight into the restructuring of the electrochemical interface is gained from first principles. Cu(100) restructuring under varying applied potentials and adsorbate coverages is studied by grand canonical density functional theory and global optimization techniques, as well as ab initio molecular dynamics and mechanistic calculations. We show that electroreduction conditions cause the formation of a shifted-row reconstruction on Cu(100), induced by hydrogen adsorption. The reconstruction is initiated at 1/6 ML H coverage, when the Cu–H bonding sufficiently weakens the Cu–Cu bonds between the top- and sublayer, and further stabilized at 1/3 ML when H adsorbates fill all the created 3-fold hollow sites. The simulated scanning tunneling microscopy (STM) images of the calculated reconstructed interfaces agree with experimentalin situSTM. However, compared to the thermodynamic prediction, the onsets of reconstruction events in the experiment occur at more negative applied voltages. This is attributed to kinetic effects in restructuring, which we describe via different statistical models, to produce the potential- and pH-dependent surface stability diagram. This manuscript provides rich atomistic insight into surface restructuring in electroreduction conditions, which is required for the understanding and design of Cu-based materials for electrocatalytic processes. It also offers the methodology to study the problem ofin situelectrode reconstruction.