Orbital Coupling of PbO7 Node in Single-Crystal Metal-Organic Framework Enhances Li-O2 Battery Electrocatalysis

Yin Zhou; Qianfeng Gu; Yinger Xin; Xinxue Tang; Haikun Wu; Shaojun Guo

doi:10.1021/acs.nanolett.3c03576

Orbital Coupling of PbO₇ Node in Single-Crystal Metal-Organic Framework Enhances Li-O₂ Battery Electrocatalysis

Yin Zhou, Qianfeng Gu, Yinger Xin, Xinxue Tang, Haikun Wu, Shaojun Guo^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

12 Citations (Scopus)

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Abstract

Optimizing the local coordination environment of metal centers in metal-organic frameworks (MOFs) is crucial yet challenging for regulating the overpotential of lithium-oxygen (Li-O₂) batteries. Herein, we report the synthesis of a class of PbO₇ nodes in a single crystal MOF (naphthalene-lead-MOF, known as Na-Pb-MOF) to significantly enhance the kinetics of both discharge and charge processes. Compared to the PbO₆ node in the single-crystal tetramethoxy-lead-MOF (4OMe-Pb-MOF), the bond length between Pb and O in the PbO₇ node of Na-Pb-MOF increases, resulting in weaker Pb 5d-O 2p orbital coupling, which optimizes the adsorption interaction toward intermediates, and thereby promotes the rate-determining steps of both the reduction of LiO₂ to Li₂O₂ and the oxidation of LiO₂ to O₂ for reducing the activation energy of the overall reaction. Consequently, Li-O₂ batteries based on Na-Pb-MOF electrocatalysts exhibit a low total charge-discharge overpotential of 0.52 V and an excellent cycle life of 140 cycles. © 2023 American Chemical Society.

Original language	English
Pages (from-to)	10600-10607
Journal	Nano Letters
Volume	23
Issue number	22
Online published	9 Nov 2023
DOIs	https://doi.org/10.1021/acs.nanolett.3c03576
Publication status	Published - 22 Nov 2023

Research Keywords

energy barrier
lithium-oxygen batteries
metal−organic framework
orbital coupling
overpotentials

Publisher's Copyright Statement

COPYRIGHT TERMS OF DEPOSITED POSTPRINT FILE: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Nano Letters, copyright © 2023 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.nanolett.3c03576.

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title = "Orbital Coupling of PbO7 Node in Single-Crystal Metal-Organic Framework Enhances Li-O2 Battery Electrocatalysis",

abstract = "Optimizing the local coordination environment of metal centers in metal-organic frameworks (MOFs) is crucial yet challenging for regulating the overpotential of lithium-oxygen (Li-O2) batteries. Herein, we report the synthesis of a class of PbO7 nodes in a single crystal MOF (naphthalene-lead-MOF, known as Na-Pb-MOF) to significantly enhance the kinetics of both discharge and charge processes. Compared to the PbO6 node in the single-crystal tetramethoxy-lead-MOF (4OMe-Pb-MOF), the bond length between Pb and O in the PbO7 node of Na-Pb-MOF increases, resulting in weaker Pb 5d-O 2p orbital coupling, which optimizes the adsorption interaction toward intermediates, and thereby promotes the rate-determining steps of both the reduction of LiO2 to Li2O2 and the oxidation of LiO2 to O2 for reducing the activation energy of the overall reaction. Consequently, Li-O2 batteries based on Na-Pb-MOF electrocatalysts exhibit a low total charge-discharge overpotential of 0.52 V and an excellent cycle life of 140 cycles. {\textcopyright} 2023 American Chemical Society.",

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author = "Yin Zhou and Qianfeng Gu and Yinger Xin and Xinxue Tang and Haikun Wu and Shaojun Guo",

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T1 - Orbital Coupling of PbO7 Node in Single-Crystal Metal-Organic Framework Enhances Li-O2 Battery Electrocatalysis

AU - Zhou, Yin

AU - Gu, Qianfeng

AU - Xin, Yinger

AU - Tang, Xinxue

AU - Wu, Haikun

AU - Guo, Shaojun

PY - 2023/11/22

Y1 - 2023/11/22

N2 - Optimizing the local coordination environment of metal centers in metal-organic frameworks (MOFs) is crucial yet challenging for regulating the overpotential of lithium-oxygen (Li-O2) batteries. Herein, we report the synthesis of a class of PbO7 nodes in a single crystal MOF (naphthalene-lead-MOF, known as Na-Pb-MOF) to significantly enhance the kinetics of both discharge and charge processes. Compared to the PbO6 node in the single-crystal tetramethoxy-lead-MOF (4OMe-Pb-MOF), the bond length between Pb and O in the PbO7 node of Na-Pb-MOF increases, resulting in weaker Pb 5d-O 2p orbital coupling, which optimizes the adsorption interaction toward intermediates, and thereby promotes the rate-determining steps of both the reduction of LiO2 to Li2O2 and the oxidation of LiO2 to O2 for reducing the activation energy of the overall reaction. Consequently, Li-O2 batteries based on Na-Pb-MOF electrocatalysts exhibit a low total charge-discharge overpotential of 0.52 V and an excellent cycle life of 140 cycles. © 2023 American Chemical Society.

AB - Optimizing the local coordination environment of metal centers in metal-organic frameworks (MOFs) is crucial yet challenging for regulating the overpotential of lithium-oxygen (Li-O2) batteries. Herein, we report the synthesis of a class of PbO7 nodes in a single crystal MOF (naphthalene-lead-MOF, known as Na-Pb-MOF) to significantly enhance the kinetics of both discharge and charge processes. Compared to the PbO6 node in the single-crystal tetramethoxy-lead-MOF (4OMe-Pb-MOF), the bond length between Pb and O in the PbO7 node of Na-Pb-MOF increases, resulting in weaker Pb 5d-O 2p orbital coupling, which optimizes the adsorption interaction toward intermediates, and thereby promotes the rate-determining steps of both the reduction of LiO2 to Li2O2 and the oxidation of LiO2 to O2 for reducing the activation energy of the overall reaction. Consequently, Li-O2 batteries based on Na-Pb-MOF electrocatalysts exhibit a low total charge-discharge overpotential of 0.52 V and an excellent cycle life of 140 cycles. © 2023 American Chemical Society.

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KW - overpotentials

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