Revised Nitrogen Reduction Scaling Relations from Potential-Dependent Modeling of Chemical and Electrochemical Steps
Revised Nitrogen Reduction Scaling Relations from Potential-Dependent Modeling of Chemical and Electrochemical Steps
复制标题
根据化学和电化学步骤的电位相关建模修正氮还原比例关系
DOI：
10.1021/acscatal.3c01978
复制
发表时间：
2023
期刊：
影响因子：
12.9
通讯作者：
Musgrave, Charles B.
中科院分区：
文献类型：
--
作者：
Tezak, Cooper R.;Singstock, Nicholas R.;Alherz, Abdulaziz W.;Vigil-Fowler, Derek;Sutton, Christopher A.;Sundararaman, Ravishankar;Musgrave, Charles B.
电化学氮气还原反应(NRR)是实现无碳氨生产的一条很有前途的途径。然而，目前催化剂的活性和选择性较差，限制了该反应的进行。合理设计优良的NRR电催化剂需要对当前材料限制的详细机理了解，以告知如何克服这些限制。目前对金属催化剂上的结垢如何限制NRR的理解是基于只考虑质子耦合电子转移(PCET)步骤的简化反应路径。在这里，我们应用巨正则密度泛函理论研究了在外加电势作用下，30个金属表面在溶剂中的NRR机理。我们应用Gmax热力学描述符的宏正则改编的Φmax来评估催化剂活性的趋势。这种方法为金属上的核反应活动标度产生了一个Φ最大“火山”图，与只考虑PCET步骤时确定的标度关系有质的不同。NH3*解吸被发现限制了火山顶部物质的NRR活性，并在逐渐降低的电位下截断了火山的峰值。这些修正的标度关系可能为合理设计性能优良的NRR电催化剂提供依据。这种方法可用于研究其他材料和反应化学，其中电化学和化学步骤都是在外加电势下模拟的。
The electrochemical nitrogen reduction reaction (NRR) is a promising route to enable carbon-free ammonia production. However, this reaction is limited by the poor activity and selectivity of current catalysts. The rational design of superior NRR electrocatalysts requires a detailed mechanistic understanding of current material limitations to inform how these might be overcome. The current understanding of how scaling limits NRR on metal catalysts is predicated on a simplified reaction pathway that considers only proton-coupled electron transfer (PCET) steps. Here, we apply grand-canonical density functional theory to investigate a more comprehensive NRR mechanism that includes both electrochemical and chemical steps on 30 metal surfaces in solvent under an applied potential. We applied Φmax, a grand-canonical adaptation of theGmaxthermodynamic descriptor, to evaluate trends in catalyst activity. This approach produces a Φmax“volcano” diagram for NRR activity scaling on metals that qualitatively differs from the scaling relations identified when only PCET steps are considered. NH3* desorption was found to limit the NRR activity for materials at the top of the volcano and truncate the volcano’s peak at increasingly reducing potentials. These revised scaling relations may inform the rational design of superior NRR electrocatalysts. This approach is transferable to study other materials and reaction chemistries where both electrochemical and chemical steps are modeled under an applied potential.
登录
查看更多内容
影响因子：
8.4
作者：
G. Hochman;A. Goldman;F. Felder;J. Mayer;Alexander J. M. Miller;Patrick L. Holland;Leo A. Goldman;Patricia Manocha;Ze Song;Saketh Aleti
通讯作者：
G. Hochman;A. Goldman;F. Felder;J. Mayer;Alexander J. M. Miller;Patrick L. Holland;Leo A. Goldman;Patricia Manocha;Ze Song;Saketh Aleti
影响因子：
6.1
作者：
Jain, Anubhav;Shyue Ping Ong;Persson, Kristin A.
通讯作者：
Persson, Kristin A.
使用从头计算和离子淌度质谱法分析糖肽离子的分子结构
DOI：
--
发表时间：
2019
期刊：
影响因子：
--
作者：
中村賀美;竹内孝江
通讯作者：
竹内孝江
钨电极上电化学氮还原和析氢动力学的计算检验
影响因子：
7.3
作者：
Árni Björn Höskuldsson;Ebrahim Tayyebi;Egill Skúlason
通讯作者：
Egill Skúlason