Abstract
Water electrolysis powered by renewable electricity can produce clean hydrogen, but the technology is limited by the slow anodic oxygen evolution reaction (OER). The most active monometallic OER catalyst is high-valence ruthenium, but it is thermodynamically unstable. Here we leverage the strong and tunable interaction between substrate and active site found in single atom catalysts, and discover a local electronic manipulation strategy for stabilizing high-valence Ru single sites (Ru SS) on a class of Ni-based phosphate porous hollow spheres (Ru SS MNiPi PHSs where M = Fe, Co, Mn, Cu) for efficient electrolysis. Both X-ray absorption fine structure and density functional theory calculation results verify the intrinsic stability of the catalyst, and suggest that this originates from the tailored valence state, coordination number and local electronic structure of the Ru SS. We formulate general guidelines for stabilizing high-valence catalytic sites and introduce a double-volcano plot to describe the superior electrocatalytic behaviours of high-valence Ru SS. The optimum Ru SS/FeNiPi achieves a low overpotential of 204 mV and 49 mV for the OER and hydrogen evolution reaction at 10 mA cm−2, respectively. Assembling Ru SS/FeNiPi in an industrial-level electrolyser with a low Ru loading of 0.081 mg cm−2 realizes a stable industrial current density of 2,000 mA cm−2 at 1.78 V, which is the highest reported value in alkaline electrolyte to the best of our knowledge, and exceeds that of commercial Pt//RuO2 by 5.7 times.
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Acknowledgements
This study was financially supported by National Science Fund for Distinguished Young Scholars (No. 52025133), National Natural Science Foundation of China (No. 52261135633), China National Petroleum Corporation-Peking University Strategic Cooperation Project of Fundamental Research, the Beijing Natural Science Foundation (No. Z220020), CNPC Innovation Found (2021DQ02-1002), New Cornerstone Science Foundation through the XPLORER PRIZE, Young Elite Scientists Sponsorship Program by CAST (2021QNRC001), the National Natural Science Foundation of China/Research Grant Council of Hong Kong Joint Research Scheme (N_PolyU502/21), Natural Science Foundation of Chongqing (CSTB2022NSCQ-MSX0557), Talent introduction of Chongqing University of Science and Technology (No. ckrc2021050, ckrc20230401), the funding for Projects of Strategic Importance of The Hong Kong Polytechnic University (Project Code: 1-ZE2V), Shenzhen Fundamental Research Scheme-General Program (JCYJ20220531090807017), the Natural Science Foundation of Guangdong Province (2023A1515012219) and Departmental General Research Fund (Project Code: ZVUL) from The Hong Kong Polytechnic University. B.H. also thanks the support from Research Centre for Carbon-Strategic Catalysis (RC-CSC), Research Institute for Smart Energy (RISE), and Research Institute for Intelligent Wearable Systems (RI-IWEAR) of The Hong Kong Polytechnic University. We thank BSRF, NSRL and SSRF for the synchrotron beam time.
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S.G. conceived the idea and designed this study. S.-Y.L. synthesized the samples, conducted characterization, electrochemical tests and performed MEA device. B.H. and M.S. conducted the calculation study. M.J. and H.L. performed XPS tests. H.Y., Q.Z. and L.G. performed HAADF-STEM imaging. M.L., P.Z., Y.C., K.Y., C.S., J.W., Y.W. and F.L. provided suggestions on the manuscript. S.G., S.-Y.L. and B.H. wrote the paper. All authors discussed the results and edited the paper.
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Nature Synthesis thanks Bo Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.
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Lu, SY., Huang, B., Sun, M. et al. Synthetic tuning stabilizes a high-valence Ru single site for efficient electrolysis. Nat. Synth (2023). https://doi.org/10.1038/s44160-023-00444-x
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DOI: https://doi.org/10.1038/s44160-023-00444-x
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