Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction,ACS Catalysis

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Coadsorption of NRR and HER Intermediates Determines the Performance of Ru-N4 toward Electrocatalytic N2 Reduction
ACS Catalysis ( IF 11.3 ) Pub Date : 2022-02-03 , DOI: 10.1021/acscatal.1c05820
Tongwei Wu _{1,

2,

3} , Marko M. Melander ₁ , Karoliina Honkala ₁

Affiliation

Electrochemical N₂ reduction (NRR) to ammonia is seriously limited by the competing hydrogen evolution reaction (HER), but atomic-scale factors controlling HER/NRR competition are unknown. Herein we unveil the mechanism, thermodynamics, and kinetics determining the HER/NRR efficiency on the state-of-the-art NRR electrocatalyst, Ru-N₄, using grand canonical ensemble density functional theory (GCE-DFT). We show that NRR/HER intermediates coadsorb on the catalyst where NRR intermediates suppress HER and selectivity is determined by the initial step forming *NNH or *H. Our results provide crucial insight into the complex NRR/HER competition, show the necessity of using GCE-DFT calculations, and suggest ways to improve NRR selectivity.

中文翻译：

NRR 和 HER 中间体的共吸附决定了 Ru-N4 对电催化 N2 还原的性能

电化学 N ₂还原 (NRR) 生成氨受到竞争性析氢反应 (HER) 的严重限制，但控制 HER/NRR 竞争的原子尺度因素尚不清楚。在这里，我们使用大规范集合密度泛函理论 (GCE-DFT)揭示了决定最先进的 NRR 电催化剂 Ru-N _{4的 HER/NRR 效率的机制、热力学和动力学。}我们表明 NRR/HER 中间体共吸附在催化剂上，其中 NRR 中间体抑制 HER，选择性由形成 *NNH 或 *H 的初始步骤决定。我们的结果为复杂的 NRR/HER 竞争提供了重要的见解，表明了使用 GCE-DFT 计算的必要性，并提出了提高 NRR 选择性的方法。

更新日期：2022-02-03

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