Single boron modulated graphdiyne nanosheets for efficient electrochemical nitrogen fixation: a first-principles study,Physical Chemistry Chemical Physics

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Single boron modulated graphdiyne nanosheets for efficient electrochemical nitrogen fixation: a first-principles study
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2022-06-24 , DOI: 10.1039/d2cp01711c
Cheng Fu ₁ , Yafei Li ₁ , Haiyan Wei ₁

Affiliation

The electroreduction of dinitrogen (N₂) is a promising alternative approach for ammonia synthesis under mild conditions. In this work, metal-free electrocatalysts using a single boron atom doped into a graphdiyne (GDY) monolayer are fabricated for N₂ fixation and conversion to NH₃. The NRR electrochemical mechanism has been examined by density functional theory (DFT) calculations. Our calculations revealed that configuration B(S₃)@GDY fabricated using a single boron substituting the diacetylene carbon atom exhibits superior catalytic activity in the nitrogen reduction reaction. The preferred distal pathway of the NRR has an extremely low limiting potential of only 0.27 V. In addition, boron atom doping in GDY results in a small band gap (0.24 eV for B(S₃)@GDY) and redistribution of the electron density. The electron deficient boron atom is largely positively charged, and thus plays a crucial role in the activation of the N [triple bond, length as m-dash]

N bond. Moreover, the competing HER is effectively suppressed. This work provides an efficient metal-free single atom electrocatalyst for the NRR based on a 2D graphdiyne monolayer.

中文翻译：

用于高效电化学固氮的单硼调制石墨二炔纳米片：第一性原理研究

二氮（N ₂）的电还原是一种在温和条件下合成氨的有前景的替代方法。在这项工作中，制造了使用掺杂到石墨二炔 (GDY) 单层中的单个硼原子的无金属电催化剂，用于 N ₂固定和转化为 NH ₃。NRR 电化学机制已通过密度泛函理论 (DFT) 计算进行了检验。我们的计算表明配置 B(S ₃)@GDY 使用单个硼取代联乙炔碳原子制造，在氮还原反应中表现出优异的催化活性。NRR 的首选远端路径具有极低的限制电位，仅为 0.27 V。此外，GDY 中的硼原子掺杂导致带隙小（B(S ₃ )@GDY 为 0.24 eV）和电子密度的重新分布. 缺电子硼原子大部分带正电，因此在 N [三键，长度为 m-dash]