Abstract
Atomically dispersed catalysts based on 3d metals have been extensively explored in the catalytic field, but stabilizing 4d and 5d metals like Ru, Pd, and Pt as single atoms remains a challenge due to their high cohesive energies. Herein, we develop a hydrogen-embrittlement-inspired strategy that leverages H2 permeation to weaken metal-metal cohesion in 4d/5d metal clusters during high-temperature synthesis. Hydrogen diffuses into the clusters, driving their dissociation into individual atoms, which are subsequently stabilized by nitrogen dopants in carbon supports, resulting in the formation of stable M-N4 single-atom sites. Taking Ru as a model system, ex-situ microscopy and spectroscopy offer definitive evidence that hydrogen permeation disrupts Ru-Ru bonding interactions, facilitating the conversion of Ru clusters into isolated RuN4 sites during the H2-assisted thermal activation process. Consequently, the prepared NC-Ru-950 catalyst achieves satisfactory activity and stability for acidic oxygen reduction and proton exchange membrane fuel cells. This work introduces a robust and universal strategy for stabilizing 4d and 5d transition metals as single-atom catalysts, offering a promising route to develop high-performance electrocatalysts.
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Shi, X. et al. Metal–support frontier orbital interactions in single-atom catalysis. Nature 640, 668–675 (2025).
Xia, C. et al. General synthesis of single-atom catalysts with high metal loading using graphene quantum dots. Nat. Chem. 13, 887–894 (2021).
Qiao, B. et al. Single-atom catalysis of CO oxidation using Pt1/FeOx. Nat. Chem. 3, 634–641 (2011).
Chen, Y. et al. Single-atom catalysts: synthetic strategies and electrochemical applications. Joule 2, 1242–1264 (2018).
Li, J. et al. Thermally driven structure and performance evolution of atomically dispersed FeN4 sites for oxygen reduction. Angew. Chem. Int. Ed. 58, 18971–18980 (2019).
Cao, Y. et al. Quantifying asymmetric coordination to correlate with oxygen reduction activity in Fe-based single-atom catalysts. Angew. Chem. Int. Ed. 64, e202423556 (2025).
Yin, S. et al. An in situ exploration of how Fe/N/C oxygen reduction catalysts evolve during synthesis under pyrolytic conditions. Nat. Commun. 15, 6229 (2024).
Liu, S. et al. Atomically dispersed iron sites with a nitrogen–carbon coating as highly active and durable oxygen reduction catalysts for fuel cells. Nat. Energy 7, 652–663 (2022).
Zeng, Y. et al. Tuning the thermal activation atmosphere breaks the activity–stability trade-off of Fe–N–C oxygen reduction fuel cell catalysts. Nat. Catal. 6, 1215–1227 (2023).
He, Y. et al. Dynamically unveiling metal–nitrogen coordination during thermal activation to design high-efficient atomically dispersed CoN4 active sites. Angew. Chem. Int. Ed. 60, 9516–9526 (2021).
Zhang, S. et al. Rational ligand design of conjugated coordination polymers for efficient and selective nitrate electroreduction to ammonia. Adv. Mater. 37, 2418681 (2025).
Li, J. et al. Atomically dispersed manganese catalysts for oxygen reduction in proton-exchange membrane fuel cells. Nat. Catal. 1, 935–945 (2018).
Chen, G. et al. Mn–N–C with high-density atomically dispersed Mn active sites for the oxygen reduction reaction. Angew. Chem. Int. Ed. 64, e202503934 (2025).
Hu, Q. et al. Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction. Nat. Commun. 13, 3958 (2022).
Deng, Z. et al. Pd 4d orbital overlapping modulation on Au@Pd nanowires for efficient H2O2 production. J. Am. Chem. Soc. 146, 2816–2823 (2024).
Takimoto, D. et al. Platinum nanosheets synthesized via topotactic reduction of single-layer platinum oxide nanosheets for electrocatalysis. Nat. Commun. 14, 19 (2023).
Yang, X. et al. Cohesive energy discrepancy drives the fabrication of multimetallic atomically dispersed materials for hydrogen evolution reaction. Nat. Commun. 15, 8216 (2024).
Assa Aravindh, S. et al. Compositional variation of magnetic moment, magnetic anisotropy energy and coercivity in Fe(1−x)Mx(M=Co/Ni) nanowires: an ab initio study. Applied Nanoscience 2, 409–415 (2012).
Tchernatinsky, A. et al. Relativistic tight-binding model: application to Pt surfaces. Phys. Rev. B 83, 205431 (2011).
Zhao, D. et al. Atomic site electrocatalysts for water splitting, oxygen reduction and selective oxidation. Chem. Soc. Rev. 49, 2215–2264 (2020).
Chang, J. et al. Synthesis of ultrahigh-metal-density single-atom catalysts via metal sulfide-mediated atomic trapping. Nat. Synth. 3, 1427–1438 (2024).
Wang, S. et al. Ligand assisted thermal atomization of palladium clusters: an inspiring approach for the rational design of atomically dispersed metal catalysts. Angew. Chem. Int. Ed. 62, e202218630 (2023).
Wei, S. et al. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms. Nat. Nanotechnol. 13, 856–861 (2018).
Mills, G. et al. Reversible work transition state theory: application to dissociative adsorption of hydrogen. Surf. Sci. 324, 305–337 (1995).
Jónsson, H. Mills, G. & Jacohsen K. W. Nudged elastic band method for finding minimum energy paths of transitions. In Classical and Quantum Dynamics in Condensed Phase Simulations, (Eds. Berne, B. J., Ciccotti, G. & Coker, D. F.) 385–404 (World Scientific Publishing Co. Pte. Ltd., 1998).
Kellogg, G. L. et al. Surface self-diffusion on Pt(001) by an atomic exchange mechanism. Phys. Rev. Lett. 64, 3143–3146 (1990).
Ravel, B. et al. ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. J. Synchrotron Radiat. 12, 537–541 (2005).
Dau, H. et al. X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers-potential and questions examined with special focus on the tetra-nuclear manganese complex of oxygenic photosynthesis. Anal. Bioanal.Chem. 376, 562–583 (2003).
Guo, P. et al. Breaking Sabatier’s vertex via switching the oxygen adsorption configuration and reaction pathway on dual active sites for acidic oxygen reduction. Energy Environ. Sci. 17, 3077–3087 (2024).
Xiao, M. et al. Engineering energy level of metal center: Ru single-atom site for efficient and durable oxygen reduction catalysis. J. Am. Chem. Soc. 141, 19800–19806 (2019).
Funke, H. et al. Wavelet analysis of extended X-ray absorption fine structure data. Phys. Rev. B 71, 094110 (2005).
Xia, Y.-F. et al. How to appropriately assess the oxygen reduction reaction activity of platinum group metal catalysts with rotating disk electrode. IScience 24, 103024 (2021).
Weiß, A. et al. Distribution of relaxation times analysis of high-temperature PEM fuel cell impedance spectra. Electrochim. Acta 230, 391–398 (2017).
Meyer, Q. et al. Operando detection of oxygen reduction reaction kinetics of Fe–N–C catalysts in proton exchange membrane fuel cells. J. Power Sources 533, 231058 (2022).
Martinez, U. et al. Durability challenges and perspective in the development of PGM-free electrocatalysts for the oxygen reduction reaction. Curr. Opin. Electroche. 9, 224–232 (2018).
Liu, S. et al. Operando deconvolution of the degradation mechanisms of iron–nitrogen–carbon catalysts in proton exchange membrane fuel cells. Energy Environ. Sci. 16, 3792–3802 (2023).
Kresse, G. et al. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).
Wu, Q. et al. Pivotal role of the Pourbaix diagram in electrocatalysis. J. Mater. Chem. A 12, 27974–27978 (2024).
Sui, R. et al. Constructing asymmetric Fe–Nb diatomic sites to enhance ORR activity and durability. J. Am. Chem. Soc. 146, 26442–26453 (2024).
Morankar, A. et al. A first principles analysis of potential-dependent structural evolution of active sites in Fe-N-C catalysts. Proc. Natl. Acad. Sci. USA 120, e2308458120 (2023).
Yang, C. et al. Dipoles effect in Fe-N-C catalyst by high-energy p orbitals for enhanced acidic oxygen reduction reaction. Angew. Chem. Int. Ed. 65, e20210 (2025).
Liu, M. et al. In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction. Nat. Commun. 15, 1675 (2024).
Jia, B. et al. Harnessing pyridinic N vacancy defect in microporous structures to induce the pre-adsorption of oxygen and boost oxygen reduction reaction kinetics. Angew. Chem. Int. Ed. 64, e202508674 (2025).
Wang, Y. et al. Si/carbon-dots with surface N-C sites promoting proton and electron transfers in oxygen reduction reaction. Angew. Chem. Int. Ed. 64, e202509790 (2025).
Song, J. et al. Supercritical CO2-assisted rapid synthesis of covalent organic framework-based electrocatalyst for efficient two-electron oxygen reduction reaction. Nat. Commun. 16, 8963 (2025).
Zhang, Y.-L. et al. Electronic delocalization regulates the occupancy and energy level of Co 3dz2 orbitals to enhance bifunctional oxygen catalytic activity. Adv. Funct. Mater. 32, 2209499 (2022).
Dai, Y. et al. Tailoring the d-orbital splitting manner of single atomic sites for enhanced oxygen reduction. Adv. Mater. 35, 2210757 (2023).
Maintz, S. et al. LOBSTER: a tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chem. 37, 1030–1035 (2016).
Maintz, S. et al. Analytic projection from plane-wave and PAW wavefunctions and application to chemical-bonding analysis in solids. J. Comput. Chem. 34, 2557–2567 (2013).
Wan, T. H. et al. Influence of the discretization methods on the distribution of relaxation times deconvolution: implementing radial basis functions with DRTtools. Electrochim. Acta 184, 483–499 (2015).
Misra, D. et al. CO2 electroreduction on single atom catalysts: the role of the DFT functional. Phys. Chem. Chem. Phys. 26, 10746–10756 (2024).
Mathew, K. et al. Implicit self-consistent electrolyte model in plane-wave density-functional theory. J. Chem. Phys. 151, 234101 (2019).
Mathew, K. et al. Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways. J. Chem. Phys. 140, 084106 (2014).
Yu, S. et al. What is the rate-limiting step of oxygen reduction reaction on Fe–N–C catalysts? J. Am. Chem. Soc. 145, 25352–25356 (2023).
Zhao, X. et al. Origin of selective production of hydrogen peroxide by electrochemical oxygen reduction. J. Am. Chem. Soc. 143, 9423–9428 (2021).
Acknowledgements
This work was supported by the National Natural Science Foundation of China (Grant No. U23A20573 (Z.-B.W.), 22409041 (Y.-L.Z.) and 22579039 (L.Z.)), the National Key Research and Development Program of China (2025YFE0114000, (Z.-B.W.)), the Key Research and Development Program of Shandong Province (2022CXGC010305, (Z.-B.W.)), Natural Science Foundation of Heilongjiang Province of China (LH2024B013, (Y.-L.Z.)), the China Postdoctoral Science Foundation (Grant No. 2025T181147, (Y.-L.Z.)), the Fundamental Research Funds for the Central Universities (Grant No. FRFCU5710051922 (L.Z.) and HIT.NSFJG202451, (Y.-L.Z.)), Guangdong Basic and Applied Basic Research Foundation (No. 2023B1515120022 and 2022B1515120001, (Z.-B.W.)), Shenzhen Science and Technology Innovation Program (No. KJZD20240903095610014 and KJZD20240903095712017, (Z.-B.W.)), and the High-Level Professional Team in Shenzhen (KQTD20210811090045006, (Z.-B.W.)). The authors express the gratitude for the significant support provided by the Electron Microscope Center of Shenzhen University and Instrumental Analysis Center of Shenzhen University.
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P.G. and Y.-K.D. conceived and designed the experiments. P.G. implemented the experiments. P.G. and B.L. (Bo Liu) finished the theoretical calculations. P.G., M.M., Z.-G.Z., and L.-X.S. conducted fuel cell tests. P.G., B.L. (Bing Liu), A.-B.C., and Z.-Y.Z. assisted materials characterization sections. P.G., Y.-K.D., Y.-L.Z., L.Z., and Z.-B.W. contributed to the writing and editing of the manuscript. All authors commented on the manuscript.
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Guo, P., Dai, Y., Zhang, Y. et al. Synthesis of atomically dispersed catalysts via hydrogen embrittlement-like assisted thermal activation for acidic oxygen reduction. Nat Commun (2026). https://doi.org/10.1038/s41467-026-71340-z
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DOI: https://doi.org/10.1038/s41467-026-71340-z
