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Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution

Nature Energy volume 1, Article number: 16184 (2016) Cite this article

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Abstract

The design and synthesis of efficient electrocatalysts are important for electrochemical conversion technologies. The oxygen evolution reaction (OER) is a key process in such conversions, having applications in water splitting and metal–air batteries. Here, we report ultrathin metal–organic frameworks (MOFs) as promising electrocatalysts for the OER in alkaline conditions. Our as-prepared ultrathin NiCo bimetal–organic framework nanosheets on glassy-carbon electrodes require an overpotential of 250 mV to achieve a current density of 10 mA cm−2. When the MOF nanosheets are loaded on copper foam, this decreases to 189 mV. We propose that the surface atoms in the ultrathin MOF sheets are coordinatively unsaturated—that is, they have open sites for adsorption—as evidenced by a suite of measurements, including X-ray spectroscopy and density-functional theory calculations. The findings suggest that the coordinatively unsaturated metal atoms are the dominating active centres and the coupling effect between Ni and Co metals is crucial for tuning the electrocatalytic activity.

High-performance electrocatalysts are key in many energy conversion and storage systems1,2,3. Presently used catalysts for the oxygen evolution reaction (OER)—a reaction central to metal–air batteries and water splitting technologies—typically require noble metal oxides, which are costly. Furthermore, large overpotentials to drive the reaction decrease the energy conversion efficiency and hinder the practical application of devices. Huge efforts have therefore been devoted to fabricate efficient, alternative homogeneous and heterogeneous electrocatalysts4,5,6. Generally, homogeneous molecular catalysts have advantages of convenient structural design and tunability, and high activity, as well as being conducive to mechanistic studies. However, poor recoverability from the reaction system seriously impedes their applications7. In contrast, heterogeneous catalysts are easily recyclable and potentially cost-effective8,9, but the number and location of active centres on solid catalyst surfaces are often indistinct, difficult to control, and prone to changes under reaction environments that not only lead to poor stability and reproducibility, but also make mechanistic studies difficult7.

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Figure 1: Physical characterization of NiCo-UMOFNs.
Figure 2: Structural characterization of NiCo-UMOFNs.
Figure 3: OER electrochemical activity of NiCo-UMOFNs.
Figure 4: Ex situ XAS characterization of local coordination of Ni/Co atoms in NiCo-UMOFNs.
Figure 5: In situ XAS characterization of NiCo-UMOFNs.
Figure 6: DFT calculation for the OER on UMOFNs.

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Acknowledgements

We appreciate the financial support from National Research Fund for Fundamental Key Project (2014CB931801 and 2016YFA0200700, Z.T.), Instrument Developing Project of the Chinese Academy of Sciences, Grant No. YZ201311, CAS-CSIRO Cooperative Research Program, Grant No. GJHZ1503, “Strategic Priority Research Program” of the Chinese Academy of Sciences (Grant No. XDA09040100), National Natural Science Foundation of China (91023007 and 20773033 (S.L.), 21025310 (Z.T.)), and the New Century Excellent Talents in University, Outstanding Young Funding of Heilongjiang Province, Jialin Xie Fundation of Institute of High Energy Physics, CAS (542016IHEPZZBS501 (J.D.)) and NSFC (Grant No. 11605225). We thank L. Gu for providing high-angle annular dark-field scanning transmission electron microscope tests. All DFT calculations were undertaken on the NCI National Facility in Canberra, Australia, which is supported by the Australian Commonwealth Government.

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Authors and Affiliations

  1. CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology, Beijing 100190, China

    Shenlong Zhao, Huajie Yin, Kun Zhao, Chao Gao, Lijuan Zhang, Jiawei Lv, Jinxin Wang, Jianqi Zhang, Abdul Muqsit Khattak, Niaz Ali Khan, Zhixiang Wei & Zhiyong Tang

  2. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150080, China

    Shenlong Zhao, Lijuan Zhang, Jinxin Wang & Shaoqin Liu

  3. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150080, China

    Shenlong Zhao, Xiaofei Zhang & Shaoqin Liu

  4. Centre for Clean Environment and Energy, Gold Coast Campus, Griffith University, Queensland 4222, Australia

    Yun Wang, Huajie Yin & Huijun Zhao

  5. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

    Juncai Dong, Pengfei An & Jing Zhang

  6. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275, China

    Chun-Ting He

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Contributions

Z.T. proposed the research direction and guided the project. S.Z., Y.W., C.-T.H. and H.Y. designed and performed the experiments. Z.T., S.Z., Y.W., J.D., C.-T.H. and P.A. analysed and discussed the experimental results and drafted the manuscript. K.Z., X.Z., C.G., L.Z., J.L., J.W., Jianqi Z., A.M.K., N.A.K., Z.W., Jing Z., S.L. and H.Z. joined the discussion of data and gave useful suggestions. Y.W., J.D. and C.-T.H. contributed equally to this work.

Corresponding authors

Correspondence to Shaoqin Liu, Huijun Zhao or Zhiyong Tang.

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The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Methods, Supplementary Figures 1–41, Supplementary Tables 1–5. (PDF 4660 kb)

Supplementary Data 1

Crystallographic information for NiCo-UMOFNs. (CIF 6 kb)

Supplementary Data 2

Crystallographic information for Ni-UMOFNs. (CIF 6 kb)

Supplementary Data 3

Crystallographic information for Co-UMOFNs. (CIF 6 kb)

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Zhao, S., Wang, Y., Dong, J. et al. Ultrathin metal–organic framework nanosheets for electrocatalytic oxygen evolution. Nat Energy 1, 16184 (2016). https://doi.org/10.1038/nenergy.2016.184

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