Influence of Local Inhomogeneities and the Electrochemical Environment on the Oxygen Reduction Reaction on Pt-Based Electrodes: A DFT Study
Influence of Local Inhomogeneities and the Electrochemical Environment on the Oxygen Reduction Reaction on Pt-Based Electrodes: A DFT Study
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DOI：
10.1021/acs.jpcc.0c09548
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发表时间：
2020-12
影响因子：
3.7
通讯作者：
S. Sakong;David Mahlberg;T. Roman;Mengru Li;Mohnish Pandey;A. Gross
中科院分区：
文献类型：
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作者：
S. Sakong;David Mahlberg;T. Roman;Mengru Li;Mohnish Pandey;A. Gross
我们已经进行了密度泛函理论计算，探索克服的线性标度关系的可能性，在氧还原反应（ORR）使用局部不均匀性Pt基表面合金，支持Pt单层，和Pt岛。我们证明，调用不等价的邻近反应位点可以克服一维线性标度关系的限制。结果，Ru（0001）衬底上的Pt岛的（111）边缘位置处的ORR活性优于平坦Pt（111）上的ORR活性。此外，我们表明，这是至关重要的，适当地考虑到电化学环境，包括适当的表面覆盖和电解质的存在下，这导致微观修改ORR反应方案和重新确定的限速步骤。
We have performed density functional theory calculations to explore the possibility to overcome the linear scaling relations in the oxygen reduction reaction (ORR) using local inhomogeneities on Pt-based surface alloys, supported Pt monolayers, and Pt islands. We demonstrate that invoking inequivalent neighboring reaction sites allows overcoming the restrictions of one-dimensional linear scaling relations. As a consequence, the ORR activity at a (111) edge site of a Pt island on a Ru(0001) substrate outperforms the one on flat Pt(111). Furthermore, we show that it is critical to appropriately take the electrochemical environment into account, including the proper surface coverage and the presence of the electrolyte, which leads to microscopically modified ORR reaction schemes and a redetermination of the rate-limiting step.