Carbon-Coordinated Single Cr Site for Efficient Electrocatalytic N2 Fixation,Advanced Theory and Simulations

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Carbon-Coordinated Single Cr Site for Efficient Electrocatalytic N2 Fixation
Advanced Theory and Simulations ( IF 2.9 ) Pub Date : 2021-04-21 , DOI: 10.1002/adts.202100044
Wei Song ₁ , Ling Fu ₂ , Chaozheng He _{3,

4} , Kun Xie ₅

Affiliation

Electrocatalytic nitrogen reduction reaction (NRR) is a very promising method for ammonia (NH₃) synthesis under ambient conditions, which can provide alternative routes to the traditional Haber–Bosch process and realize green NH₃ synthesis. In this study, the electrocatalytic performance of chromium (Cr) atom anchored to graphyne (Cr@GY) is systematically investigated using density functional theory (DFT) calculations. The results show that Cr@GY is an efficient NRR electrocatalyst which can activate the inert N≡N bond sufficiently. In particular, the enzymatic mechanism is considered as the most positive catalytic pathway with the limiting potential of −0.52 V. More importantly, Cr@GY can restrict a competitive hydrogen evolution reaction (HER). The electronic properties including Bader charge, the charge difference density (CDD), the partial density of states (PDOS) and the crystal orbital Hamilton population (COHP) have been analyzed in detail. In addition, the co-doping of B and N atoms in GY is beneficial to reduce the energy barrier of the potential-determining step (PDS) and promote the smooth progress of the NRR. This work can provide theoretical guidance for the experimental synthesis of the single-atom catalysts (SACs) with high activity and stability.

中文翻译：

用于高效电催化 N2 固定的碳配位单 Cr 位点

电催化氮还原反应 (NRR) 是一种非常有前景的常温合成氨 (NH ₃ ) 方法，可为传统的 Haber-Bosch 工艺提供替代路线，实现绿色 NH ₃合成。在这项研究中，使用密度泛函理论 (DFT) 计算系统地研究了锚定在石墨炔 (Cr@GY) 上的铬 (Cr) 原子的电催化性能。结果表明，Cr@GY是一种高效的NRR电催化剂，可以充分激活惰性N≡N键。特别是，酶促机制被认为是最积极的催化途径，极限电位为 -0.52 V。更重要的是，Cr@GY 可以限制竞争性析氢反应（HER）。详细分析了包括Bader电荷、电荷差密度(CDD)、部分态密度(PDOS)和晶体轨道哈密顿布居(COHP)在内的电子性质。此外，GY中B和N原子的共掺杂有利于降低电位决定步骤（PDS）的能垒，促进NRR的顺利进行。该工作可为实验合成具有高活性和稳定性的单原子催化剂（SACs）提供理论指导。

更新日期：2021-06-05

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