Xue Xiangdong, Gao Hongyi, Liu Jiangtao, Yang Ming, Feng Shihao, Liu Zhimeng, Lin Jing, Kasemchainan Jitti, Wang Linmeng, Jia Qilu, Wang Ge
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory of Function Materials for Molecule & Structure Construction, School of Materials Science and Engineering, University of Science and Technology Beijing Beijing 100083 PR China
State Key Laboratory of Advanced Chemical Power Sources, Guizhou Meiling Power Sources Co., Ltd. Zunyi Guizhou 563003 PR China.
Chem Sci. 2022 Oct 18;13(44):13160-13171. doi: 10.1039/d2sc04898a. eCollection 2022 Nov 16.
Metal-organic frameworks (MOFs) provide opportunities for the design of high-efficiency catalysts attributed to their high compositional and structural tunability. Meanwhile, the huge number of MOFs poses a great challenge to experimental-intensive development of high-performance functional applications. By taking the computationally feasible and structurally representative trigonal prismatic secondary building units (SBUs) of MOFs as the entry point, we introduce a descriptor-based approach for designing high-performance MOFs for the oxygen evolution reaction (OER). The electrostatic potential-derived charge (ESPC) is identified as a robust and universal OER performance descriptor of MOFs, showing a distinct linear relationship with the onset potentials of OER elemental steps. Importantly, we establish an ESPC-based physical pattern of active site-intermediate binding strength, which interprets the rationality of ESPC as an OER performance descriptor. We further reveal that the SBUs with Ni/Cu as active site atoms while Mn/Fe/Co/Ni as spectator atoms have excellent OER activity through the variation pattern of ESPC along with metal composition. The universal correlation between ESPC and OER activity provides a rational rule for designing high-performance MOF-based OER electrocatalysts and can be easily extended to design functional MOFs for a rich variety of catalytic applications.
金属有机框架材料（MOFs）因其高度的组成和结构可调性为高效催化剂的设计提供了契机。与此同时，大量的MOFs给高性能功能应用的实验密集型开发带来了巨大挑战。我们以MOFs计算上可行且结构具有代表性的三角棱柱次级构筑单元（SBUs）为切入点，引入一种基于描述符的方法来设计用于析氧反应（OER）的高性能MOFs。静电势衍生电荷（ESPC）被确定为MOFs一种稳健且通用的OER性能描述符，与OER元素步骤的起始电位呈现出明显的线性关系。重要的是，我们建立了基于ESPC的活性位点-中间体结合强度物理模式，解释了ESPC作为OER性能描述符的合理性。通过ESPC随金属组成的变化模式，我们进一步揭示了以Ni/Cu作为活性位点原子而以Mn/Fe/Co/Ni作为旁观原子的SBUs具有优异的OER活性。ESPC与OER活性之间的普遍相关性为设计高性能的基于MOF的OER电催化剂提供了合理规则，并且可以轻松扩展用于设计适用于各种催化应用的功能性MOFs。
