Abstract
Metastable nanomaterials, such as single-atom and high-entropy systems, with exciting physical and chemical properties are increasingly important for next-generation technologies. Here, we developed a hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis (GAUSS) platform for the preparation of metastable nanomaterials. The GAUSS platform can reach an ultra-high reaction temperature of 3,286 K within 8 ms, a rate exceeding 105 K s−1. Controlling the composition and chemistry of the hydrogen-substituted graphdiyne aerogel framework, the reaction temperature can be tuned from 1,640 K to 3,286 K. We demonstrate the versatility of the GAUSS platform with the successful synthesis of single atoms, high-entropy alloys and high-entropy oxides. Electrochemical measurements and density functional theory show that single atoms synthesized by GAUSS enhance the lithium–sulfur redox reaction kinetics in all-solid-state lithium–sulfur batteries. Our design of the GAUSS platform offers a powerful way to synthesize a variety of metastable nanomaterials.
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The data that support this study are included in the article and/or supplementary information. Any additional materials and data are available from the corresponding authors on reasonable request.
References
Sun, W., Dacek, S., Ping Ong, S., Persson, K. & Ceder, G. The thermodynamic scale of inorganic crystalline metastability. Sci. Adv. 2, e1600225 (2016).
Stein, A., Keller, S. W. & Mallouk, T. E. Turning down the heat: design and mechanism in solid-state synthesis. Science 259, 1558–1564 (1993).
Yao, Y. et al. Carbothermal shock synthesis of high-entropy-alloy nanoparticles. Science 359, 1489–1494 (2018).
Yao, Y. et al. High-throughput, combinatorial synthesis of multimetallic nanoclusters. Proc. Natl Acad. Sci. USA 117, 6316–6322 (2020).
Zhou, G. et al. Theoretical calculation guided design of single-atom catalysts toward fast kinetic and long-life Li-S batteries. Nano Lett. 20, 1252–1261 (2020).
Tian, H. et al. High-power lithium-selenium batteries enabled by atomic cobalt electrocatalyst in hollow carbon cathode. Nat. Commun. 11, 5025 (2020).
Lun, Z. et al. Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries. Nat. Mater. 20, 214–221 (2021).
Pan, Q. et al. Gradient-cell–structured high-entropy alloy with exceptional strength and ductility. Science 374, 984–989 (2021).
Li, Z., Pradeep, K. G., Deng, Y., Raabe, D. & Tasan, C. C. Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off. Nature 534, 227–230 (2016).
Wei, H. et al. Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth. Nat. Commun. 8, 1490 (2017).
Xia, C. et al. General synthesis of single-atom catalysts with high metal loading using graphene quantum dots. Nat. Chem. 13, 887–894 (2021).
Xie, P. et al. Highly efficient decomposition of ammonia using high-entropy alloy catalysts. Nat. Commun. 10, 4011 (2019).
Du, Z. et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J. Am. Chem. Soc. 141, 3977–3985 (2019).
Jiang, K. et al. Isolated Ni single atoms in graphene nanosheets for high-performance CO2 reduction. Energy Environ. Sci. 11, 893–903 (2018).
Kitchen, H. J. et al. Modern microwave methods in solid-state inorganic materials chemistry: from fundamentals to manufacturing. Chem. Rev. 114, 1170–1206 (2014).
Chen, C. H. et al. Ruthenium-based single-atom alloy with high electrocatalytic activity for hydrogen evolution. Adv. Energy Mater. 9, 1803913 (2019).
Feng, J. et al. Unconventional alloys confined in nanoparticles: building blocks for new matter. Matter 3, 1646–1663 (2020).
Wang, X. et al. Continuous 2,000 K droplet-to-particle synthesis. Mater. Today 35, 106–114 (2020).
Yang, Y. et al. Aerosol synthesis of high entropy alloy nanoparticles. Langmuir 36, 1985–1992 (2020).
Qiao, H. et al. Scalable synthesis of high entropy alloy nanoparticles by microwave heating. ACS Nano 15, 14928–14937 (2021).
Xie, H. et al. A high-temperature pulse method for nanoparticle redispersion. J. Am. Chem. Soc. 142, 17364–17371 (2020).
Li, H. et al. Nano high-entropy materials: synthesis strategies and catalytic applications. Small Struct. 1, 2000033 (2020).
Wang, C. et al. A general method to synthesize and sinter bulk ceramics in seconds. Science 368, 521–526 (2020).
Gao, X., Liu, H., Wang, D. & Zhang, J. Graphdiyne: synthesis, properties, and applications. Chem. Soc. Rev. 48, 908–936 (2019).
Du, R. et al. CMP aerogels: ultrahigh-surface-area carbon-based monolithic materials with superb sorption performance. Adv. Mater. 26, 8053–8058 (2014).
Xue, Y. et al. Anchoring zero valence single atoms of nickel and iron on graphdiyne for hydrogen evolution. Nat. Commun. 9, 1460 (2018).
Yao, Y. et al. High temperature shockwave stabilized single atoms. Nat. Nanotechnol. 14, 851–857 (2019).
Yao, S. & Zhang, X. Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction. Science 357, 389–393 (2017).
Zhang, H. et al. Designer anion enabling solid-state lithium-sulfur batteries. Joule 3, 1689–1702 (2019).
Gao, X. et al. All-solid-state lithium-sulfur batteries enhanced by redox mediators. J. Am. Chem. Soc. 143, 18188–18195 (2021).
Yao, Y. et al. Computationally aided, entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts. Sci. Adv. 6, eaaz0510 (2020).
Yang, H. et al. Carbon dioxide electroreduction on single-atom nickel decorated carbon membranes with industry compatible current densities. Nat. Commun. 11, 593 (2020).
Zhu, Y. et al. A cocoon silk chemistry strategy to ultrathin N-doped carbon nanosheet with metal single-site catalysts. Nat. Commun. 9, 3861 (2018).
Yang, H. et al. A universal ligand mediated method for large scale synthesis of transition metal single atom catalysts. Nat. Commun. 10, 4585 (2019).
Wan, J. et al. Ultrathin, flexible, solid polymer composite electrolyte enabled with aligned nanoporous host for lithium batteries. Nat. Nanotechnol. 14, 705–711 (2019).
Mortensen, J. J., Hansen, H. A. & Jacobsen, K. Real-space grid implementation of the projector augmented wave method. Phys. Rev. B 71, 035109 (2005).
Enkovaara, J. et al. Electronic structure calculations with GPAW: a real-space implementation of the projector augmented-wave method. J. Phys. Condens Matter 22, 253202 (2010).
Berland, K. & Hyldgaard, P. Exchange functional that tests the robustness of the plasmon description of the van der Waals density functional. Phys. Rev. B 89, 035412 (2014).
Acknowledgements
This work was jointly supported by the US Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering (contract no. DE-AC02-76SF00515) and the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies, of the US Department of Energy under the Battery Materials Research (BMR) Program and the Battery500 Consortium program. We acknowledge H. Gong for freeze drying of the HGDY aerogel. Use of the Stanford Synchrotron Radiation Light Source, SLAC National Accelerator Laboratory, is supported by the US DOE, Office of Science, Office of Basic Energy Sciences under contract DE-AC02-76SF00515. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS-2026822. Characterization done by the UCI team (R.Z. and H.L.X.) was supported by the National Science Foundation under award number CHE-1900401 and H.L.X.’s startup funding. We acknowledge the use of facilities and instrumentation at the UC Irvine Materials Research Institute (IMRI), which is supported in part by the National Science Foundation through the UC Irvine Center for Complex and Active Materials (DMR-2011967). Part of the work was supported by the Office of Naval Research under agreement number N00014-22-1-2489.
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Y.C., Xueli Zheng and X.G. conceived the idea. Y.C. supervised the project. Xueli Zheng and X.G. designed and carried out all the experiments. Xueli Zheng, X.G., Y.J. and Xiaolin Zheng helped with high-speed video and thermal video measurements. R.A.V., R.Z. and H.L.X. performed S/TEM measurements. X.X. performed gas chromatography experiments. R.X. performed COMSOL simulations. J.W. carried out DFT calculations. Y.Y. performed XPS measurements. P.Z., Y.Y. and L.C.G. assisted with materials synthesis. All authors discussed the results and assisted during manuscript preparation.
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Zheng, X., Gao, X., Vilá, R.A. et al. Hydrogen-substituted graphdiyne-assisted ultrafast sparking synthesis of metastable nanomaterials. Nat. Nanotechnol. 18, 153–159 (2023). https://doi.org/10.1038/s41565-022-01272-4
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DOI: https://doi.org/10.1038/s41565-022-01272-4
