Missing-linker metal-organic frameworks for oxygen evolution reaction

Ziqian Xue; Kang Liu; Qinglin Liu; Yinle Li; Manrong Li; Cheng-Yong Su; Naoki Ogiwara; Hirokazu Kobayashi; Hiroshi Kitagawa; Min Liu; Guangqin Li

doi:10.1038/s41467-019-13051-2

Missing-linker metal-organic frameworks for oxygen evolution reaction

Nat Commun. 2019 Nov 6;10(1):5048. doi: 10.1038/s41467-019-13051-2.

Authors

Ziqian Xue¹, Kang Liu², Qinglin Liu¹, Yinle Li¹, Manrong Li¹, Cheng-Yong Su¹, Naoki Ogiwara³, Hirokazu Kobayashi^{3

4}, Hiroshi Kitagawa³, Min Liu⁵, Guangqin Li⁶

Affiliations

¹ MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, 510275, Guangzhou, China.
² State Key Laboratory of Powder Metallurgy, Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, 932 South Lushan Road, 410083, Changsha, Hunan, China.
³ Division of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo-ku, Kyoto, 606-8502, Japan.
⁴ JST, PRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan.
⁵ State Key Laboratory of Powder Metallurgy, Institute of Super-microstructure and Ultrafast Process in Advanced Materials, School of Physics and Electronics, Central South University, 932 South Lushan Road, 410083, Changsha, Hunan, China. minliu@csu.edu.cn.
⁶ MOE Laboratory of Bioinorganic and Synthetic Chemistry, Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, 510275, Guangzhou, China. liguangqin@mail.sysu.edu.cn.

Abstract

Metal-organic frameworks (MOFs) have been recognized as compelling platforms for the development of miscellaneous applications because of their structural diversity and functional tunability. Here, we propose that the electrocatalytic properties could be well modified by incorporating missing linkers into the MOF. Theoretical calculations suggest the electronic structure of MOFs can be tuned by introducing missing linkers, which improves oxygen evolution reaction (OER) performance of the MOF. Inspired by these aspects, we introduced various missing linkers into a layered-pillared MOF Co₂(OH)₂(C₈H₄O₄) (termed as CoBDC) to prepare missing-linker MOFs. Transmission electron microscope and synchrotron X-ray measurements confirmed that the missing linkers in the MOF could be introduced and well controlled by our strategy. The self-supported MOF nanoarrays with missing linkers of carboxyferrocene exhibit excellent OER performance with ultralow overpotential of 241 mV at 100 mA cm^-2. This work opens a new prospect to develop efficient MOF-based electrocatalysts by introducing missing linkers.

Publication types

Research Support, Non-U.S. Gov't