Stable Multifunctional Single-Atom Catalysts Resulting from the Synergistic Effect of Anchored Transition-Metal Atoms and Host Covalent–Organic Frameworks,The Journal of Physical Chemistry C

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Stable Multifunctional Single-Atom Catalysts Resulting from the Synergistic Effect of Anchored Transition-Metal Atoms and Host Covalent–Organic Frameworks
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-07-21 , DOI: 10.1021/acs.jpcc.0c04360
Juan Wang ₁ , Junru Wang ₁ , Siyun Qi ₁ , Mingwen Zhao ₁

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Noble-metal-free electrocatalysts for highly efficient hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) are highly demanded in energy conversion and storage techniques. The single-atom catalytic (SAC) technique emerged as a promising strategy to reach this goal but is currently facing obstacles such as migration and aggregation of active atoms and low metal loading. We demonstrated from first principles that the two-dimensional (2D) covalent organic frameworks (COFs) of phthalocyanines and pyrazine linkages can firmly anchor transition-metal (TM) atoms. The resultant TM-embedded COFs (TM-COFs) exhibit multifunctional electrocatalytic activity for HER, OER, and ORR, which can be attributed to the synergistic effect of the anchored TM atoms and COFs. Specifically, Mn- and Cr-COFs are predicted to have extremely low overpotentials of −0.014/0.44/0.31 and −0.239/0.35/0.29 V for HER/OER/ORR, which are comparable or even superior to those of the well-developed noble catalysts. We also proposed the electron transfer Δδ from TM atom to the framework and p-band center ε_p of carbon atoms as descriptors for the adsorption strength of intermediates on the TM-COF monolayers. In view of the recent experimental progress on the synthesis of the TM-COFs, these computational results offer not only economical alternatives of noble catalysts but also a promising strategy for the design of multifunctional electrocatalysts.

中文翻译：

固定化过渡金属原子与主体共价有机框架协同效应产生的稳定的多功能单原子催化剂

在能量转换和存储技术中，非常需要用于高效氢析出反应（HER），氧析出反应（OER）和氧还原反应（ORR）的无贵金属电催化剂。单原子催化（SAC）技术是实现该目标的一种有前途的策略，但目前正面临诸如活性原子的迁移和聚集以及低金属负载等障碍。我们从第一个原理证明了酞菁和吡嗪键的二维（2D）共价有机骨架（COF）可以牢固地锚定过渡金属（TM）原子。生成的TM嵌入的COF（TM-COF）对HER，OER和ORR表现出多功能的电催化活性，这可以归因于锚定的TM原子和COF的协同作用。特别，预测HER / OER / ORR的Mn-和Cr-COF具有-0.014 / 0.44 / 0.31和-0.239 / 0.35 / 0.29 V的极低超电势，与发达的贵金属催化剂相比甚至更高。我们还提出了从TM原子到骨架和p带中心ε的电子转移Δδ碳原子的_p作为TM-COF单层上中间体吸附强度的指标。鉴于最近在合成TM-COFs方面的实验进展，这些计算结果不仅为贵族催化剂提供了经济的替代方案，而且为多功能电催化剂的设计提供了有希望的策略。

更新日期：2020-08-14

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