Abstract
Single-atom catalysts (SACs) exhibit exceptional intrinsic activity per metal site, but are often limited by low metal loading, which compromises the overall catalytic performance. Pyrolytic strategies commonly used for synthesizing SACs generally suffer from aggregation at high metal loadings. Here we report a universal synthesis approach for ultrahigh-density metal–nitrogen–carbon (UHDM–N–C) SACs via a metal-sulfide-mediated atomization process. We show that our approach is general for transition, rare-earth and noble metals, achieving 17 SACs with metal loadings >20 wt% (including a loading of 26.9 wt% for Cu, 31.2 wt% for Dy and 33.4 wt% for Pt) at 800 °C, as well as high-entropy quinary and vicenary SACs with ultrahigh metal contents. In situ X-ray diffraction and transmission electron microscopy alongside molecular simulations reveals a dynamic nanoparticle-to-single atom transformation process, including thermally driven decomposition of the metal sulfide and the trapping of liberated metal atoms to form thermodynamically stable M–N–C moieties. Our studies indicate that a high N-doping is crucial for achieving ultrahigh-loading metal atoms and a metal-sulfide-mediated process is essential for avoiding metal aggregation at high loadings. As a demonstration, the metal-loading-dependent activity in electrocatalytic oxygen evolution reaction is demonstrated on SACs with increasing Ni content.
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Acknowledgements
This work was partly supported by the National Natural Science Foundation of China (NSFC, nos. 52122308 52202050, 21905253 and 51973200), the China Postdoctoral Science Foundation (2022TQ0286), the Natural Science Foundation of Henan (202300410372) and the Joint Fund of Science and Technology R&D Plan of Henan Province (232301420042). We also acknowledge the Beijing Synchrotron Radiation Facility and the Center for Modern Analysis and Gene Sequencing of Zhengzhou University for supporting this research. G.I.N.W. acknowledges funding support from the Ministry of Business Innovation and Employment (C05X2007 and UOCX2118) and the Royal Society Te Apārangi (James Cook Research Fellowship). X.Y. acknowledges the Leverhulme Trust for Early Career Fellowship for support.
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S.L., X.D., B.Y., Z.T. and J.C. designed and coordinated the project and also supervised all aspects of the research. W.J. conducted the materials synthesis, structural characterizations of the prepared catalysts and electrochemical measurements, interpreted the data and drafted the paper. X.Y., A.C. and J.Y. carried out the corresponding DFT calculations. S.W. assisted with the in situ experimental investigations. Data collection and analyses were performed by W.J., H.W., C.W. and S.W. G.I.N.W. participated in discussions about the experimental results and providing valuable suggestions for the research. All authors contributed to the preparation and editing of the paper.
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Nature Synthesis thanks Christodoulos Chatzichristodoulou, Yuen Wu 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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Supplementary Figs. 1–81, Discussion, Notes 1–7 and Tables 1–5.
Supplementary Video 1
A movie shows the dynamic decomposition process of the Ni3S3 nanoparticle.
Supplementary Video 2
A movie shows the dynamic decomposition process of the Ni8S8 nanoparticle.
Supplementary Video 3
A movie shows the dynamic atomization evolution by theoretical simulation, where the emitted Ni atom is trapped by the N-dopants to form a thermodynamically stable Ni−N4−C site.
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Chang, J., Jing, W., Yong, X. et al. Synthesis of ultrahigh-metal-density single-atom catalysts via metal sulfide-mediated atomic trapping. Nat. Synth 3, 1427–1438 (2024). https://doi.org/10.1038/s44160-024-00607-4
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DOI: https://doi.org/10.1038/s44160-024-00607-4
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