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A strongly coupled Ru–CrOx cluster–cluster heterostructure for efficient alkaline hydrogen electrocatalysis

Nature Catalysis volume 7, pages 441–451 (2024)Cite this article

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Abstract

Constructing well-defined heterostructure interfaces in catalysts is an efficient strategy to break the so-called scaling relationships and to accelerate the reactions involving multiple intermediates. Here a cluster–cluster heterostructure catalyst composed of crystalline ruthenium cluster and amorphous chromium oxide cluster is designed to realize high-performance alkaline hydrogen electrocatalysis. The strongly coupled cluster–cluster heterostructure interface induces a unique interfacial interpenetration effect, which simultaneously optimizes the adsorption of intermediates on each cluster. The resulting catalyst exhibits impressive catalytic activities for the hydrogen oxidation reaction (exchange current density of 2.8 A mg−1Ru) and the hydrogen evolution reaction (mass activity of 23.0 A mg−1Ru at the overpotential of 100 mV) in alkaline media. The hydroxide exchange membrane fuel cell delivers a mass activity of 22.4 A mg−1Ru at 0.65 V and outstanding durability with no voltage loss over 105 h operation at 500 mA cm−2. The present work demonstrates the superiority of cluster–cluster heterostructure interface towards the development of advanced catalysts.

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Fig. 1: Schematic illustration.
Fig. 2: Structural characterizations of Ru–CrOx@CN.
Fig. 3: Fine structural characterizations.
Fig. 4: Electrochemical HOR performance and HEMFCs performance.
Fig. 5: Electrochemical HER performance.
Fig. 6: Mechanism investigation.

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Data availability

The data supporting the findings of this study are available within the article and its Supplementary Information files. All data is available from the authors upon reasonable request. The atomic coordinates of the computational models are given in Supplementary Data 1.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (no. 2022YFB4002503), the National Natural Science Foundation of China (no. 92261119 and 52171224), the Natural Science Foundation of Zhejiang Province (grant no. LZ22B030006), the Research Grant Council of the Hong Kong Special Administrative Region (C6011-20G), the Innovation and Technology Commission of the Hong Kong Special Administrative Region (no. ITC-CNERC14EG03). B.Z. acknowledges support from China Postdoctoral Science Foundation (no. 2021M692757), the National Postdoctoral Program for Innovative Talents (no. BX2021251) and Zhejiang Provincial Natural Science Foundation (no. LQ23E010005). The authors thank beamline BL11B and BL14W1 of the Shanghai Synchrotron Radiation Facility (SSRF) for providing the XAFS beamtime, and Photoemission End-Station (BL10B) at the National Synchrotron Radiation Laboratory (NSRL) for NEXAFS beamtime.

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Authors and Affiliations

  1. School of Materials Science and Engineering, Zhejiang University, Hangzhou, P. R. China

    Bingxing Zhang, Jianmei Wang, Danqing Liu, Yaping Chen, Mingxia Gao, Yongfeng Liu, Hongge Pan & Wenping Sun

  2. Department of Chemical and Biological Engineering, The Hong Kong University of Science and Technology, Kowloon, China

    Bingxing Zhang, Guimei Liu & Minhua Shao

  3. Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, USA

    Catherine M. Weiss & Yushan Yan

  4. State Key Laboratory of Silicate Materials for Architectures, International School of Materials Science and Engineering, Wuhan University of Technology, Wuhan, P. R. China

    Lixue Xia

  5. School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen, China

    Peng Zhou

  6. Institute of Science and Technology for New Energy, Xi’an Technological University, Xi’an, P. R. China

    Jian Chen & Hongge Pan

  7. Energy Institute, and Chinese National Engineering Research Center for Control and Treatment of Heavy Metal Pollution, The Hong Kong University of Science and Technology, Kowloon, China

    Minhua Shao

  8. State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, P. R. China

    Wenping Sun

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Contributions

B.Z. performed the catalyst development, characterizations and performance evaluation. J.W., D.L., Y.C. and J.C. helped in electrocatalysis experiments and material characterizations. G.L. and C.M.W. helped in fuel cell test. L.X. and P. Z. helped in DFT calculations. HP., M.G., Y.L., Y.Y., M.S., W.S. and B.Z. analysed the data. All the authors contributed to the overall scientific discussions and edited the manuscript. W.S., H.P. and B.Z. conceived the idea and co-wrote the paper.

Corresponding authors

Correspondence to Hongge Pan or Wenping Sun.

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Nature Catalysis thanks Ligang Feng, Marion Giraud and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–44, Tables 1–11, notes and References 1–60.

Supplementary Data 1

Atomic coordinates of the initial and final configurations of the trajectories in AIMD simulations.

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Zhang, B., Wang, J., Liu, G. et al. A strongly coupled Ru–CrOx cluster–cluster heterostructure for efficient alkaline hydrogen electrocatalysis. Nat Catal 7, 441–451 (2024). https://doi.org/10.1038/s41929-024-01126-3

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