Single-Atom Electrocatalysis for Hydrogen Evolution Based on the Constant Charge and Constant Potential Models,The Journal of Physical Chemistry Letters

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Single-Atom Electrocatalysis for Hydrogen Evolution Based on the Constant Charge and Constant Potential Models
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2022-07-28 , DOI: 10.1021/acs.jpclett.2c01288
Siyu Tan ₁ , Yujin Ji ₁ , Youyong Li _{1,

2}

Affiliation

DFT calculations are performed at constant charge, while practical electrochemical reactions often take place under constant potential. To unravel the effect of the model difference on single-atom electrocatalysis, we implement benchmarked DFT and grand-canonical DFT calculations to systematically investigate the hydrogen adsorption on 99 single-atom M–N_xC_y motifs. We find that the initial electrode potentials for all M–N_xC_y are negative, leading to the loss of system electrons once their electrode potentials are fixed at 0 V/SHE. We prove that the quantitive difference of ΔG(*H) between the CCM and CPM is proportional to the square difference of total charge change before and after H adsorption, which originates from the adjustment of electronic occupation states. Our work provides theoretical insight into the differential capacitance model in the graphene-confining SACs for the HER and emphasizes the importance of CPM for in silico design of electrocatalysts.

中文翻译：

基于恒电荷恒电位模型的单原子电催化析氢

DFT 计算是在恒定电荷下进行的，而实际的电化学反应通常在恒定电位下进行。为了揭示模型差异对单原子电催化的影响，我们实施了基准 DFT 和大规范 DFT 计算，以系统地研究 99 个单原子 M-N _x C _y基序上的氢吸附。我们发现所有 M-N _x C _y的初始电极电位都是负的，一旦它们的电极电位固定在 0 V/SHE，就会导致系统电子的损失。我们证明了 Δ G的数量差异CCM 和 CPM 之间的 (*H) 与 H 吸附前后总电荷变化的平方差成正比，这源于电子占据状态的调整。我们的工作为 HER 的石墨烯限制 SAC 中的微分电容模型提供了理论见解，并强调了 CPM在电子催化剂设计中的重要性。

更新日期：2022-07-28

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