Scalable ruthenium core–shell hydrogen catalyst for efficient and robust proton-exchange membrane electrolyser
Source abstract
Abstract
The reliance on platinum-based hydrogen catalysts in proton-exchange membrane water electrolysers compromises cost efficiency. Here we develop a non-platinum catalyst composite featuring a ruthenium oxide (RuO2) core encapsulated by a thin ruthenium phosphide (RuP2) shell, rapidly synthesized by a flame-assisted process. This core-shell catalyst demonstrates good performance towards hydrogen evolution in acidic media, achieving an overpotential of 16 mV at 10 mA cm-2 at a low loading of 5.5 wt%. Mechanistic studies and density functional theory show that the RuO2/RuP2 core-shell structure optimizes interfacial-water organization, enhancing proton transfer at the reaction interface and boosting hydrogen evolution activity. We further demonstrate the scalable synthesis of this Ru catalyst via colloidal milling, enabling bulk production of this catalyst (tens of grams per batch) under mild conditions. When integrating Ru catalyst prepared at this scale into a practical proton-exchange membrane electrolyser (2 × 100 cm-2), it sustains 200 A (1 A cm-2) at a moderate cell voltage (1.8 V) with a stability over 1,500 h. Our results suggest a possible cost-effective alternative for proton-exchange membrane electrolysis.
Source: europepmc · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: Electrocatalysts for Energy Conversion · Hybrid Renewable Energy Systems · Metalloenzymes and iron-sulfur proteins
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (54)
Show source-provided references
1. Dresselhaus, M. S. & Thomas, I. L. Alternative energy technologies. Nature 414, 332–337 (2001).10.1038/35104599 ↗
2. Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).10.1126/science.1103197 ↗
3. Li, A. et al. Atomically dispersed hexavalent iridium oxide from MnO2 reduction for oxygen evolution catalysis. Science 384, 666–670 (2024).10.1126/science.adg5193 ↗
4. Chu, S. & Majumdar, A. Opportunities and challenges for a sustainable energy future. Nature 488, 294–303 (2012).10.1038/nature11475 ↗
5. Zhou, S., Shi, L., Li, Y., Yang, T. & Zhao, S. Metal-organic framework-based electrocatalysts for acidic water splitting. Adv. Funct. Mater. 34, 2400767 (2024).10.1002/adfm.202400767 ↗
6. Luo, Y. et al. Material engineering strategies for efficient hydrogen evolution reaction catalysts. Small Methods 8, 2400158 (2024).10.1002/smtd.202400158 ↗
7. Li, Z., Ge, R., Su, J. & Chen, L. Recent progress in low Pt content electrocatalysts for hydrogen evolution reaction. Adv. Mater. Interfaces 7, 2000396 (2020).10.1002/admi.202000396 ↗
8. Chen, J. et al. Diversity of platinum-sites at platinum/fullerene interface accelerates alkaline hydrogen evolution. Nat. Commun. 14, 1711 (2023).10.1038/s41467-023-37404-0 ↗
9. Ma, T. et al. Crystalline lattice-confined atomic Pt in metal carbides to match electronic structures and hydrogen evolution behaviors of platinum. Adv. Mater. 34, 2206368 (2022).10.1002/adma.202206368 ↗
10. Hu, Q. et al. Subnanometric Ru clusters with upshifted D band center improve performance for alkaline hydrogen evolution reaction. Nat. Commun. 13, 3958 (2022).10.1038/s41467-022-31660-2 ↗
11. Yu, Q. et al. Hydroxyapatite-derived heterogeneous Ru-Ru2P electrocatalyst and environmentally-friendly membrane electrode toward efficient alkaline electrolyser. Small 19, 2208045 (2023).10.1002/smll.202208045 ↗
12. Xu, J. et al. Boosting the hydrogen evolution performance of ruthenium clusters through synergistic coupling with cobalt phosphide. Energy Environ. Sci. 11, 1819–1827 (2018).10.1039/C7EE03603E ↗
13. Tao, L. et al. Precise synthetic control of exclusive ligand effect boosts oxygen reduction catalysis. Nat. Commun. 14, 6893 (2023).10.1038/s41467-023-42514-w ↗
14. Li, M. et al. Exclusive strain effect boosts overall water splitting in PdCu/Ir core/shell nanocrystals. Angew. Chem. Int. Ed. 60, 8243–8250 (2021).10.1002/anie.202016199 ↗
15. Yao, N. et al. Atomically dispersed Ru oxide catalyst with lattice oxygen participation for efficient acidic water oxidation. Chem 9, 1882–1896 (2023).10.1016/j.chempr.2023.03.005 ↗
16. Liu, H. et al. Eliminating over-oxidation of ruthenium oxides by niobium for highly stable electrocatalytic oxygen evolution in acidic media. Joule 7, 558–573 (2023).10.1016/j.joule.2023.02.012 ↗
17. Du, H. et al. Unlocking interfacial electron transfer of ruthenium phosphides by homologous core–shell design toward efficient hydrogen evolution and oxidation. Adv. Mater. 34, 2204624 (2022).10.1002/adma.202204624 ↗
18. Li, W. et al. Designing Ru–B–Cr moieties to activate the Ru site for acidic water electrolysis under industrial-level current density. Nano Lett. 25, 443–452 (2025).10.1021/acs.nanolett.4c05113 ↗
19. Jin, Y. et al. The role of phosphorus on alkaline hydrogen oxidation electrocatalysis for ruthenium phosphides. Angew. Chem. Int. Ed. 63, e202406888 (2024).10.1002/anie.202406888 ↗
20. Hansen, J. N. et al. Is there anything better than Pt for HER? ACS Energy Lett. 6, 1175–1180 (2021).10.1021/acsenergylett.1c00246 ↗
21. Xu, Z. et al. Phosphorus-induced anti-growth of ruthenium clusters-single atoms for ultra-stable hydrogen evolution over 100,000 cycles. Joule 8, 1790–1803 (2024).10.1016/j.joule.2024.03.005 ↗
22. Zheng, Y., Jiao, Y., Jaroniec, M. & Qiao, S. Z. Advancing the electrochemistry of the hydrogen-evolution reaction through combining experiment and theory. Angew. Chem. Int. Ed. 54, 52–65 (2015).10.1002/anie.201407031 ↗
23. Wang, D. et al. Dual modulation of hydroxyl action on ruthenium surface by single-atom supports for alkaline H2 evolution. Adv. Funct. Mater. 35, 2417976 (2024).10.1002/adfm.202417976 ↗
24. Lu, Z. et al. Ultrahigh hydrogen evolution performance of under-water “superaerophobic” MoS2 nanostructured electrodes. Adv. Mater. 26, 2683–2687 (2014).10.1002/adma.201304759 ↗
25. Tufvesson, P., Lima-Ramos, J., Nordblad, M. & Woodley, J. M. Guidelines and cost analysis for catalyst production in biocatalytic processes. Org. Process Res. Dev. 15, 266–274 (2011).10.1021/op1002165 ↗
26. Van Allsburg, K. M., Tan, E. C. D., Super, J. D., Schaidle, J. A. & Baddour, F. G. Early-stage evaluation of catalyst manufacturing cost and environmental impact using CatCost. Nat. Catal. 5, 342–353 (2022).10.1038/s41929-022-00759-6 ↗
27. Sharma, R., Gyergyek, S. & Andersen, S. M. Critical thinking on baseline corrections for electrochemical surface area (ECSA) determination of Pt/C through H-adsorption/H-desorption regions of a cyclic voltammogram. Appl Catal. B 311, 121351 (2022).10.1016/j.apcatb.2022.121351 ↗
28. Li, J. et al. A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution. Nat. Commun. 12, 3502 (2021).10.1038/s41467-021-23750-4 ↗
29. Karlsson, R. K. B., Cornell, A. & Pettersson, L. G. M. Structural changes in RuO2 during electrochemical hydrogen evolution. J. Phys. Chem. C 120, 7094–7102 (2016).10.1021/acs.jpcc.5b11696 ↗
30. Cheng, F. et al. Accelerated water activation and stabilized metal-organic framework via constructing triangular active-regions for ampere-level current density hydrogen production. Nat. Commun. 13, 6486 (2022).10.1038/s41467-022-34278-6 ↗
31. Krishtalik, L. I. Kinetic isotope effect in the hydrogen evolution reaction. Electrochim. Acta 46, 2949–2960 (2001).10.1016/S0013-4686(01)00526-6 ↗
32. Zhu, S. et al. Reconstructing hydrogen-bond network for efficient acidic oxygen evolution. Angew. Chem. Int. Ed. 63, e202319462 (2024).10.1002/anie.202319462 ↗
33. Chen, X. et al. Revealing the role of interfacial water and key intermediates at ruthenium surfaces in the alkaline hydrogen evolution reaction. Nat. Commun. 14, 5289 (2023).10.1038/s41467-023-41030-1 ↗
34. Shen, L.-F. et al. Interfacial structure of water as a new descriptor of the hydrogen evolution reaction. Angew. Chem. Int. Ed. 59, 22397–22402 (2020).10.1002/anie.202007567 ↗
35. Deng, L. et al. Lewis acid-mediated interfacial water supply for sustainable proton exchange membrane water electrolysis. J. Am. Chem. Soc. 146, 35438–35448 (2024).10.1021/jacs.4c14529 ↗
36. Marx, D., Tuckerman, M. E., Hutter, J. & Parrinello, M. The nature of the hydrated excess proton in water. Nature 397, 601–604 (1999).10.1038/17579 ↗
37. Nørskov, J. K. et al. Trends in the exchange current for hydrogen evolution. J. Electrochem. Soc. 152, 0931–7597 (2005).10.1149/1.1856988 ↗
38. De Grotthuss, C. et al. Memoir on the decomposition of water and of the bodies that it holds in solution by means of galvanic electricity. Ann. Chim. 1757, 871–875 (2006).
39. Cong, D., Sun, J. & Pan, Y. Hydrogen-bond-network breakdown boosts selective CO2 photoreduction by suppressing H2 evolution. Angew. Chem. Int. Ed. 136, e202316991 (2024).10.1002/ange.202316991 ↗
40. Tang, F., Qiu, D. Y. & Wu, X. Optical absorption spectroscopy probes water wire and its ordering in a hydrogen-bond network. Phys. Rev. 15, 011048 (2025).10.1103/PhysRevX.15.011048 ↗
41. Wang, Y.-m. et al. Atomic-scale understanding of electrified interfacial structures and dynamics during the oxygen reduction reaction on the Fe-N4/C electrocatalyst. ACS Catal. 13, 11080–11090 (2023).10.1021/acscatal.3c02169 ↗
42. Evans, D. G. & Duan, X. Preparation of layered double hydroxides and their applications as additives in polymers, as precursors to magnetic materials and in biology and medicine. Chem. Commun. 5, 485–496 (2006).10.1039/B510313B ↗
43. Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquidmetals. Phys. Rev. B Condens. Matter 47, 558–561 (1993).10.1103/PhysRevB.47.558 ↗
44. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).10.1103/PhysRevLett.77.3865 ↗
45. Grimme, S., Ehrlich, S. & Goerigk, L. Effect of the damping function in dispersion corrected density functional theory. J. Comput. Chem. 32, 1456–1465 (2011).10.1002/jcc.21759 ↗
46. Yu, S., Levell, Z., Jiang, Z., Zhao, X. & Liu, Y. What is the rate limiting step of oxygen reduction reaction on Fe-N-C catalysts? J. Am. Chem. Soc. 145, 25352–25356 (2023).10.1021/jacs.3c09193 ↗
47. Lin, X. et al. Hydrated deep eutectic electrolytes for high-performance Zn-ion batteries capable of low-temperature operation. Adv. Funct. Mater. 32, 2109322 (2022).10.1002/adfm.202109322 ↗
48. Mathew, K., Kolluru, V. S. C., Mula, S., Steinmann, S. N. & Hennig, R. G. Implicit self-consistent electrolyte model in plane-wave density-functional theory. J. Chem. Phys. 151, 234101 (2019).10.1063/1.5132354 ↗
49. Kumar, R., Schmidt, J. R. & Skinner, J. L. Hydrogen bonding definitions and dynamics in liquid water. J. Chem. Phys. 126, 204107 (2007).10.1063/1.2742385 ↗
50. Wang, F. T., Liu, X. & Cheng, J. Water structures and anisotropic dynamics at Pt (211)/water interface revealed by machine learning molecular dynamics. Mater. Futures 3, 041001 (2024).10.1088/2752-5724/ad7619 ↗
51. Li, P. et al. Hydrogen bond network connectivity in the electric double layer dominates the kinetic pH effect in hydrogen electrocatalysis on Pt. Nat. Catal. 5, 900–911 (2022).10.1038/s41929-022-00846-8 ↗
52. Woo, T. K., Margl, P. M., Blöchl, P. E. & Ziegler, T. A combined car−parrinello QM/MM implementation for ab initio molecular dynamics simulations of extended systems: application to transition metal catalysis. J. Phys. Chem. B 101, 7877–7880 (1997).10.1021/jp9717296 ↗
53. Jarzynski, C. et al. Nonequilibrium equality for free energy differences. Phys. Rev. Lett. 78, 2690–2693 (1997).10.1103/PhysRevLett.78.2690 ↗
54. Momma, K. & Izumi, F. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011).10.1107/S0021889811038970 ↗