Two-Dimensional Organometallic Frameworks with Pyridinic Single-Metal-Atom Sites for Bifunctional ORR/OER,Advanced Functional Materials

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Two-Dimensional Organometallic Frameworks with Pyridinic Single-Metal-Atom Sites for Bifunctional ORR/OER
Advanced Functional Materials ( IF 18.5 ) Pub Date : 2022-08-11 , DOI: 10.1002/adfm.202207110
Tianyang Liu ₁ , Yu Wang ₁ , Yafei Li ₁

Affiliation

Achieving efficient bifunctional oxygen reduction and evolution reactions (ORR/OER) on non-noble metal catalysts is desirable but remains a significant challenge. Herein, inspired by the experimentally synthesized (phen₂N₂)FeCl molecule, a stable 2D organometallic framework, namely (phen₂N₂)FeCl monolayer, is proposed as a qualified candidate by means of constant-potential first-principles computations. Unlike most 2D organometallic frameworks that feature pyrrolic coordination, the (phen₂N₂)FeCl monolayer exhibits a pyridinic-type FeN₄ ligation environment. The unique structure of the monolayer enables a high single-atom Fe loading in a heterogeneous system, superior to the typical FeNC materials. Constant-potential energy analysis and microkinetic modeling demonstrate that the monolayer holds great potential for facilitating bifunctional ORR/OER in both the acidic and alkaline conditions, showing theoretical activity higher than the FeNC materials, (phen₂N₂)FeCl molecule, and Pt/IrO₂. Moreover, (phen₂N₂)MCl monolayers (M = Mn, Co, and Ni) are explored, and the (phen₂N₂)MnCl monolayer is also identified to have excellent bifunctional activity. This study highlights the rational design of local coordination environments for boosting the electrocatalytic performance of 2D organometallic frameworks.

中文翻译：

用于双功能 ORR/OER 的具有吡啶单金属原子位点的二维有机金属框架

在非贵金属催化剂上实现高效的双功能氧还原和析出反应 (ORR/OER) 是可取的，但仍然是一项重大挑战。在此，受实验合成的 (phen ₂ N ₂ )FeCl 分子的启发，通过恒电位第一性原理计算，提出了一种稳定的二维有机金属骨架，即 (phen ₂ N ₂ )FeCl 单层作为合格的候选者。与大多数以吡咯配位为特征的二维有机金属骨架不同，(phen ₂ N ₂ )FeCl 单层呈现出吡啶型 FeN ₄结扎环境。单层的独特结构能够在异质系统中实现高单原子 Fe 负载，优于典型的 Fe  N  C 材料。恒电位能量分析和微动力学模型表明，单层在酸性和碱性条件下都具有促进双功能 ORR/OER 的巨大潜力，显示出高于 Fe  N  C 材料 (phen ₂ N ₂ )FeCl 分子的理论活性, 和 Pt/IrO ₂。此外，探索了 (phen ₂ N ₂ )MCl 单分子层 (M = Mn、Co 和 Ni)，以及 (phen ₂ N ₂)MnCl 单层也被认为具有优异的双功能活性。本研究强调了局部配位环境的合理设计，以提高二维有机金属框架的电催化性能。

更新日期：2022-08-11

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