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Nanoporous nickel with rich adsorbed oxygen for efficient alkaline hydrogen evolution electrocatalysis

具有丰富吸附氧的纳米多孔镍用于高效碱性析氢电催化

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Abstract

Sluggish water dissociation kinetics severely limits the rate of alkaline electrocatalytic hydrogen evolution reaction (HER). Therefore, finding highly active electrocatalysts and clarifying the mechanism of water dissociation are challenging but important. In this study, we report an integrated nanoporous nickel (np-Ni) catalyst with high alkaline HER performance and the origin of the corresponding enhanced catalytic activity. In 1 mol L−1 KOH solution, this np-Ni electrode shows an HER overpotential of 20 mV at 10 mA cm−2, along with fast water dissociation kinetics. The excellent performance is not only attributed to the large surface area provided by the three-dimensional interconnected conductive network but also from the enhanced intrinsic activity induced by the unique surface properties. Further studies reveal that the types of oxygen species that naturally form on the Ni surface play a key role in water dissociation. Remarkably, when the lattice oxygen almost disappears, the Ni surface terminates with adsorbed oxygen (Oads), exhibiting the fastest water dissociation kinetics. Density functional theory calculation suggests that when Oads acts as the surface termination of Ni metal, the orientation and configuration of polar water molecules are strongly affected by Oads. Finally, the H—OH bond of interfacial water molecules is effectively activated in a manner similar to hydrogen bonding. This work not only identifies a high-performance and low-cost electrocatalyst but also provides new insights into the chemical processes underlying water dissociation, thus benefiting the rational design of electrocatalysts.

摘要

迟缓的水解离动力学严重限制了碱性电催化析氢反应的速率. 寻找高活性电催化剂, 并阐明水的解离机制具有挑战性和必要性. 本文通过对Ni45Zr35Ti20金属玻璃前驱体进行表面脱合金处理, 制备了一体式纳米多孔镍(nanoporous nickel, np-Ni)电极. 在1 mol L−1 KOH溶液中, 该np-Ni电极在10 mA cm−2电流密度下显示出20 mV的析氢过电位和快速的水解离动力学. 优异的性能不仅源于三维互连的导电网络提供的大表面积, 还源于其独特的表面性质带来的本征催化活性的增强. 进一步研究表明, 镍表面天然形成的氧组分类型对水分子的解离有重要影响. 特别是, 当晶格氧原子几乎消失时, 镍表面以吸附氧原子终止, 并表现出最快的水离解动力学. 密度泛函理论计算表明, 吸附氧原子作 为镍金属的表面终止时, 附近的极性H2O分子的取向和构型会受到吸附氧的强烈影响. 最终, 界面水分子的H–OH键可以以类似于氢键的方式被有效激活. 这项工作不仅提供了一种高性能/低成本的电催化剂,而且深入研究了水解离的化学过程, 有利于电催化剂的合理设计.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51571151, 51701139, 51671143, 52177220, and 51804216).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin, 300072, China

    Qingfeng Hu  (胡庆丰), Jiajun Wang  (王嘉骏), Xuerong Zheng  (郑学荣), Xiaopeng Han  (韩晓鹏), Yida Deng  (邓意达) & Wenbin Hu  (胡文彬)

  2. State Key Laboratory of Marine Resource Utilization in South China Sea, School of Materials Science and Engineering, Hainan University, Haikou, 570228, China

    Zelin Chen  (陈泽霖) & Yida Deng  (邓意达)

  3. Joint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New City, Fuzhou, 350207, China

    Jiajun Wang  (王嘉骏) & Wenbin Hu  (胡文彬)

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  1. Qingfeng Hu  (胡庆丰)
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  2. Zelin Chen  (陈泽霖)
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  5. Xiaopeng Han  (韩晓鹏)
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Contributions

Author contributions Hu Q and Chen Z designed and engineered the samples; Hu Q performed the experiments; Zheng X, Han X, and Hu W helped analyze the results; Hu Q wrote the paper with support from Deng Y. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Zelin Chen  (陈泽霖) or Yida Deng  (邓意达).

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

Additional information

Qingfeng Hu is a PhD student at the School of Materials Science and Engineering, Tianjin University. His recent research interests focus on the electrocatalytic hydrogen evolution behavior of transition metals and their derivatives with micro-nano structures in alkaline environments.

Zelin Chen received his PhD degree in material science from Tianjin University in 2020, under the supervision of Prof. Wenbin Hu and Prof. Yida Deng. At present, he works as a lecturer at the School of Materials Science and Engineering, Hainan University. His research interests include the design and controllable synthesis of noble-metal-based nanomaterials, the regulation of their surface and interface at the nanoscale, and their electrocatalytic applications in fuel cells.

Yida Deng was included in the “Changjiang Scholar Program” in 2021 and moved from Tianjin University to Hainan University as a chair professor. He received his PhD degree in materials science from Shanghai Jiao Tong University in 2006. Prof. Deng has extensive experience in the controllable synthesis of efficient electrocatalysts for energy storage and conversion, including noble and non-precious metallic nanomaterials, as well as their derivatives.

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

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Hu, Q., Chen, Z., Wang, J. et al. Nanoporous nickel with rich adsorbed oxygen for efficient alkaline hydrogen evolution electrocatalysis. Sci. China Mater. 65, 1825–1832 (2022). https://doi.org/10.1007/s40843-021-1949-9

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  • DOI: https://doi.org/10.1007/s40843-021-1949-9

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