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Stabilization of MOF-derived Co3S4 nanoparticles via graphdiyne coating for efficient oxygen evolution

石墨炔涂层稳定MOF衍生物Co3S4纳米材料用于高效 电催化析氧反应

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Abstract

Develo** a facile approach to fabricate robust electrocatalysts for the oxygen evolution reaction (OER) is essential for water electrolysis for hydrogen production. Transition metal-organic frameworks (MOFs), with their diverse coordination geometries, offer a promising avenue for deriving materials with excellent electrocatalytic properties. Leveraging the distinct controllable synthesis features of two-dimension graphdiyne (2D-GDY), we herein present a novel strategy: Loading GDY in situ onto a MOF-derived Co3S4/nickel foam (NF) material to create a self-supported electrode, GDY/Co3S4/NF, exhibiting significantly enhanced electrocatalytic performances for OER. Our comprehensive investigation reveals that GDY/Co3S4/NF demonstrates superior performance, with a low overpotential of 223 mV at a current density of 10 mA cm−2 and a small Tafel slope of 46.5 mV dec−1. Notably, it showcases exceptional stability over 45 h of continuous electrolysis at a high current density of 100 mA cm−2 under alkaline conditions, highlighting its promising practical applicability. These results validate that the unique acetylene bonds and macroporous structure of 2D-GDY enable strong electronic interactions with Co3S4, thereby tuning the electronic configuration, facilitating efficient charge transport channels, increasing active surface areas, and enhancing durability. Furthermore, in-situ attenuated total reflection surface-enhanced infrared spectroscopy (in-situ ATR-SEIRAS) analysis reveals that the synergistic effect between GDY and Co3S4 promotes the adsorption of crucial intermediate species such as OOH⋆, thereby significantly improving the electrocatalytic activity for OER. This work presents a facile and efficient strategy for constructing advanced nanomaterials with extraordinary electrocatalytic performance, offering promising prospects for various practical applications.

摘要

制备高效的OER电催化剂对水裂解制氢至关重要. 具有丰富配位 构型的MOFs可以衍生出各种优良的电催化材料. 由于石墨炔(GDY)具 有独特的可控合成特性, 我们将其原位复合在MOF衍生的Co3S4/NF材 料上, 获得了自支撑电极GDY/Co3S4/NF, 大大提高了其OER催化性能. 研究表明, GDY/Co3S4/NF在10 mA cm−2电流密度下表现出223 mV的低 过电位, 在100 mA cm−2的大电流密度下, 能够稳定电解45小时左右, 该 材料显示出了巨大的实际应用潜力. 结果表明, 由于GDY独特的炔键和 大孔结构, 它可以通过**电子相互作用与Co3S4相互作用, 从而调节电 子结构并提供有效的电荷转移通道, 从而大大提高了其电催化OER的 性能.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22375148) and the National Key R&D Program of China (2022YFA1502902).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. School of Materials Science and Engineering, Tian** University of Technology, Tian**, 300384, China

    Mengyu Lu  (陆梦玉), **n Zhao  (赵欣), Shifu Zhang  (张士福), Hengxin Jian  (蹇恒欣), Mei Wang  (王梅) & Tongbu Lu  (鲁统部)

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  1. Mengyu Lu  (陆梦玉)
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  2. **n Zhao  (赵欣)
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  4. Hengxin Jian  (蹇恒欣)
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Contributions

Author contributions Lu M and Zhang S designed and engineered the samples; Lu M, Zhao X and Zhang S performed the experiments; Jian H did some analyses. Wang M and Lu M wrote the paper with support from Lu T. Lu T and Wang M administrated the project, supervised the experiments and reviewed the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Mei Wang  (王梅) or Tongbu Lu  (鲁统部).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Mengyu Lu is a graduate student at the School of Materials Science and Engineering, Tian** University of Technology. She received her BE degree from the Jiangxi University of Science and Technology in 2022. She is mainly engaged in the application of metal-based nanomaterials in electrocatalysis.

Mei Wang received her PhD degree in 2009 at the Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. Then she worked as a postdoctoral fellow at Max-Planck Institute for Chemical Energy Conversion. She is currently an associate professor at Tian** University of Technology, working on metalbased complexes and nanomaterials synthesis, and exploring their applications in electrocatalysis.

Tongbu Lu obtained his BS in 1988 and PhD in 1993 from Lanzhou University. He joined the Sun Yat-Sen University and became a professor in 2000. In 2016, he moved to Tian** University of Technology. His current research interest focuses on the study of artificial photosynthesis, including the design of homogeneous and heterogeneous catalysts for water splitting and CO2 reduction. He obtained the National Natural Science Foundation for Distinguished Youth Scholar in 2006.

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Lu, M., Zhao, X., Zhang, S. et al. Stabilization of MOF-derived Co3S4 nanoparticles via graphdiyne coating for efficient oxygen evolution. Sci. China Mater. 67, 1882–1890 (2024). https://doi.org/10.1007/s40843-024-2956-9

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