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Monitoring oxygen production on mass-selected iridium–tantalum oxide electrocatalysts

Nature Energy volume 7, pages 55–64 (2022)Cite this article

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Abstract

Development of low-cost and high-performance oxygen evolution reaction catalysts is key to implementing polymer electrolyte membrane water electrolysers for hydrogen production. Iridium-based oxides are the state-of-the-art acidic oxygen evolution reaction catalysts but still suffer from inadequate activity and stability, and iridium’s scarcity motivates the discovery of catalysts with lower iridium loadings. Here we report a mass-selected iridium–tantalum oxide catalyst prepared by a magnetron-based cluster source with considerably reduced noble-metal loadings beyond a commercial IrO2 catalyst. A sensitive electrochemistry/mass-spectrometry instrument coupled with isotope labelling was employed to investigate the oxygen production rate under dynamic operating conditions to account for the occurrence of side reactions and quantify the number of surface active sites. Iridium–tantalum oxide nanoparticles smaller than 2 nm exhibit a mass activity of 1.2 ± 0.5 kA gIr–1 and a turnover frequency of 2.3 ± 0.9 s−1 at 320 mV overpotential, which are two and four times higher than those of mass-selected IrO2, respectively. Density functional theory calculations reveal that special iridium coordinations and the lowered aqueous decomposition free energy might be responsible for the enhanced performance.

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Fig. 1: Preparation and characterization of mass-selected Ir–Ta NPs.
Fig. 2: Monitoring oxygen evolution on gold-supported mass-selected Ir0.1Ta0.9O2.45 NPs.
Fig. 3: Comparison of OER catalytic performance.
Fig. 4: Stability of mass-selected Ir0.1Ta0.9O2.45 NPs.
Fig. 5: Isotope labelling coupled with EC-MS-determined surface active sites and TOF values of mass-selected Ir0.1Ta0.9O2.45 NPs.
Fig. 6: Theoretical analysis of OER activity and stability.

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Data availability

The authors declare that all data supporting the findings of this study are available within the paper and its Supplementary Information files and on DTU Data (https://doi.org/10.11583/DTU.16818703.v1). Source data are provided with this paper.

References

  1. Seh, Z. W. et al. Combining theory and experiment in electrocatalysis: insights into materials design. Science 355, eaad4998 (2017).

    Article  Google Scholar 

  2. Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2017).

    Article  Google Scholar 

  3. Ayers, K. E. et al. Research advances towards low cost, high efficiency PEM electrolysis. ECS Trans. 33, 3–15 (2010).

    Article  Google Scholar 

  4. Kibsgaard, J. & Chorkendorff, I. Considerations for the scaling-up of water splitting catalysts. Nat. Energy 4, 430–433 (2019).

  5. Carmo, M., Fritz, D. L., Mergel, J. & Stolten, D. A comprehensive review on PEM water electrolysis. Int. J. Hydrog. Energy 38, 4901–4934 (2013).

    Article  Google Scholar 

  6. Escudero-Escribano, M. et al. Importance of surface IrOx in stabilizing RuO2 for oxygen evolution. J. Phys. Chem. B 122, 947–955 (2018).

    Article  Google Scholar 

  7. Vesborg, P. C. & Jaramillo, T. F. Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy. RSC Adv. 2, 7933–7947 (2012).

    Article  Google Scholar 

  8. Bernt, M. et al. Current challenges in catalyst development for PEM water electrolyzers. Chem. Ing. Tech. 92, 31–39 (2020).

    Article  Google Scholar 

  9. Oakton, E. et al. IrO2-TiO2: a high-surface-area, active, and stable electrocatalyst for the oxygen evolution reaction. ACS Catal. 7, 2346–2352 (2017).

    Article  Google Scholar 

  10. da Silva, G. C. et al. Oxygen evolution reaction on tin oxides supported iridium catalysts: do we need dopants? ChemElectroChem 7, 2330–2339 (2020).

    Article  Google Scholar 

  11. Wu, G. et al. A general synthesis approach for amorphous noble metal nanosheets. Nat. Commun. 10, 4855 (2019).

    Article  Google Scholar 

  12. Seitz, L. C. et al. A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction. Science 353, 1011–1014 (2016).

    Article  Google Scholar 

  13. Nong, H. N. et al. A unique oxygen ligand environment facilitates water oxidation in hole-doped IrNiOx core–shell electrocatalysts. Nat. Catal. 1, 841–851 (2018).

    Article  Google Scholar 

  14. Spoeri, C., Kwan, J. T. H., Bonakdarpour, A., Wilkinson, D. P. & Strasser, P. The stability challenges of oxygen evolving catalysts: towards a common fundamental understanding and mitigation of catalyst degradation. Angew. Chem. Int. Ed. 56, 5994–6021 (2017).

    Article  Google Scholar 

  15. Oakton, E. et al. A simple one-pot Adams method route to conductive high surface area IrO2–TiO2 materials. New J. Chem. 40, 1834–1838 (2016).

    Article  Google Scholar 

  16. Card, H. Potential barriers to electron tunnelling in ultra-thin films of SiO2. Solid State Commun. 14, 1011–1014 (1974).

    Article  Google Scholar 

  17. Valden, M., Lai, X. & Goodman, D. W. Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties. Science 281, 1647–1650 (1998).

    Article  Google Scholar 

  18. Kim, Y.-T. et al. Balancing activity, stability and conductivity of nanoporous core-shell iridium/iridium oxide oxygen evolution catalysts. Nat. Commun. 8, 1449 (2017).

    Article  Google Scholar 

  19. Suntivich, J., May, K. J., Gasteiger, H. A., Goodenough, J. B. & Shao-Horn, Y. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles. Science 334, 1383–1385 (2011).

    Article  Google Scholar 

  20. Roy, C. et al. Impact of nanoparticle size and lattice oxygen on water oxidation on NiFeOxHy. Nat. Catal. 1, 820–829 (2018).

    Article  Google Scholar 

  21. Trimarco, D. B. et al. Enabling real-time detection of electrochemical desorption phenomena with sub-monolayer sensitivity. Electrochim. Acta 268, 520–530 (2018).

    Article  Google Scholar 

  22. Diaz-Morales, O., Calle-Vallejo, F., de Munck, C. & Koper, M. T. Electrochemical water splitting by gold: evidence for an oxide decomposition mechanism. Chem. Sci. 4, 2334–2343 (2013).

    Article  Google Scholar 

  23. Cherevko, S., Zeradjanin, A. R., Keeley, G. P. & Mayrhofer, K. J. A comparative study on gold and platinum dissolution in acidic and alkaline media. J. Electrochem. Soc. 161, H822–H830 (2014).

    Article  Google Scholar 

  24. Krempl, K. et al. Dynamic interfacial reaction rates from electrochemistry–mass spectrometry. Anal. Chem. 93, 7022–7028 (2021).

    Article  Google Scholar 

  25. Wang, Z., Guo, X., Montoya, J. & Norskov, J. K. Predicting aqueous stability of solid with computed Pourbaix diagram using SCAN functional. npj Comput. Mater. 6, 160 (2020).

    Article  Google Scholar 

  26. Regmi, Y. N. et al. Supported oxygen evolution catalysts by design: toward lower precious metal loading and improved conductivity in proton exchange membrane water electrolyzers. ACS Catal. 10, 13125–13135 (2020).

    Article  Google Scholar 

  27. Geiger, S. et al. The stability number as a metric for electrocatalyst stability benchmarking. Nat. Catal. 1, 508–515 (2018).

    Article  Google Scholar 

  28. Chen, Y. et al. Exceptionally active iridium evolved from a pseudo-cubic perovskite for oxygen evolution in acid. Nat. Commun. 10, 572 (2019).

    Article  Google Scholar 

  29. Zhang, R. et al. First example of protonation of Ruddlesden–Popper Sr2IrO4: a route to enhanced water oxidation catalysts. Chem. Mater. 32, 3499–3509 (2020).

    Article  Google Scholar 

  30. Trasatti, S. & Petrii, O. Real surface area measurements in electrochemistry. J. Electroanal. Chem. 327, 353–376 (1992).

    Article  Google Scholar 

  31. Binninger, T., Fabbri, E., Kötz, R. & Schmidt, T. J. Determination of the electrochemically active surface area of metal-oxide supported platinum catalyst. J. Electrochem. Soc. 161, H121–H128 (2013).

    Article  Google Scholar 

  32. Scott, S. B., Kibsgaard, J., Vesborg, P. C. & Chorkendorff, I. Tracking oxygen atoms in electrochemical CO oxidation—part II: lattice oxygen reactivity in oxides of Pt and Ir. Electrochim. Acta 374, 137844 (2021).

    Article  Google Scholar 

  33. Herrada, R. A. et al. Characterization of Ti electrodes electrophoretically coated with IrO2–Ta2O5 films with different Ir:Ta molar ratios. J. Alloy. Compd 862, 158015 (2021).

    Article  Google Scholar 

  34. Man, I. C. et al. Universality in oxygen evolution electrocatalysis on oxide surfaces. ChemCatChem 3, 1159–1165 (2011).

    Article  Google Scholar 

  35. Rossmeisl, J., Qu, Z.-W., Zhu, H., Kroes, G.-J. & Nørskov, J. K. Electrolysis of water on oxide surfaces. J. Electroanal. Chem. 607, 83–89 (2007).

    Article  Google Scholar 

  36. Willinger, E., Massué, C., Schlögl, R. & Willinger, M. G. Identifying key structural features of IrOx water splitting catalysts. J. Am. Chem. Soc. 139, 12093–12101 (2017).

    Article  Google Scholar 

  37. Wan, G. et al. Amorphization mechanism of SrIrO3 electrocatalyst: how oxygen redox initiates ionic diffusion and structural reorganization. Sci. Adv. 7, eabc7323 (2021).

    Article  Google Scholar 

  38. Singh, A. K. et al. Electrochemical stability of metastable materials. Chem. Mater. 29, 10159–10167 (2017).

    Article  Google Scholar 

  39. Schlossmacher, P., Klenov, D., Freitag, B. & Von Harrach, H. Enhanced detection sensitivity with a new windowless XEDS system for AEM based on silicon drift detector technology. Microsc. Today 18, 14–20 (2010).

    Article  Google Scholar 

  40. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).

    Article  Google Scholar 

  41. Hammer, B., Hansen, L. B. & Norskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999).

    Article  Google Scholar 

  42. Lee, S.-H., Kim, J., Kim, S.-J., Kim, S. & Park, G.-S. Hidden structural order in orthorhombic Ta2O5. Phys. Rev. Lett. 110, 235502 (2013).

    Article  Google Scholar 

  43. Ong, S. P. et al. Python Materials Genomics (pymatgen): a robust, open-source Python library for materials analysis. Comput. Mater. Sci. 68, 314–319 (2013).

    Article  Google Scholar 

  44. Sun, J., Ruzsinszky, A. & Perdew, J. P. Strongly constrained and appropriately normed semilocal density functional. Phys. Rev. Lett. 115, 036402 (2015).

    Article  Google Scholar 

  45. Paoli, E. A. et al. Oxygen evolution on well-characterized mass-selected Ru and RuO2 nanoparticles. Chem. Sci. 6, 190–196 (2015).

    Article  MathSciNet  Google Scholar 

  46. Alia, S. M., Shulda, S., Ngo, C., Pylypenko, S. & Pivovar, B. S. Iridium-based nanowires as highly active, oxygen evolution reaction electrocatalysts. ACS Catal. 8, 2111–2120 (2018).

    Article  Google Scholar 

  47. Jensen, A. W. et al. Self-supported nanostructured iridium-based networks as highly active electrocatalysts for oxygen evolution in acidic media. J. Mater. Chem. A 8, 1066–1071 (2020).

    Article  Google Scholar 

  48. Li, R. et al. IrW nanochannel support enabling ultrastable electrocatalytic oxygen evolution at 2 A cm−2 in acidic media. Nat. Commun. 12, 3540 (2021).

    Article  Google Scholar 

  49. Nong, H. N., Gan, L., Willinger, E., Teschner, D. & Strasser, P. IrOx core-shell nanocatalysts for cost- and energy-efficient electrochemical water splitting. Chem. Sci. 5, 2955–2963 (2014).

    Article  Google Scholar 

  50. Oh, H.-S. et al. Electrochemical catalyst–support effects and their stabilizing role for IrOx nanoparticle catalysts during the oxygen evolution reaction. J. Am. Chem. Soc. 138, 12552–12563 (2016).

    Article  Google Scholar 

  51. Debe, M. et al. Initial performance and durability of ultra-low loaded NSTF electrodes for PEM electrolyzers. J. Electrochem. Soc. 159, K165–K176 (2012).

    Article  Google Scholar 

  52. Lee, Y., Suntivich, J., May, K. J., Perry, E. E. & Shao-Horn, Y. Synthesis and activities of rutile IrO2 and RuO2 nanoparticles for oxygen evolution in acid and alkaline solutions. J. Phys. Chem. Lett. 3, 399–404 (2012).

    Article  Google Scholar 

  53. Grimaud, A. et al. Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction. Nat. Energy 2, 16189 (2016).

    Article  Google Scholar 

  54. Shan, J. et al. Charge-redistribution-enhanced nanocrystalline Ru@IrOx electrocatalysts for oxygen evolution in acidic media. Chem 5, 445–459 (2019).

    Article  Google Scholar 

  55. Gao, J. et al. Breaking long-range order in iridium oxide by alkali ion for efficient water oxidation. J. Am. Chem. Soc. 141, 3014–3023 (2019).

    Article  Google Scholar 

  56. Choi, S. et al. Pt dopant: controlling the Ir oxidation states toward efficient and durable oxygen evolution reaction in acidic media. Adv. Funct. Mater. 30, 2003935 (2020).

    Article  Google Scholar 

  57. Kim, J. et al. High-performance pyrochlore-type yttrium ruthenate electrocatalyst for oxygen evolution reaction in acidic media. J. Am. Chem. Soc. 139, 12076–12083 (2017).

    Article  Google Scholar 

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Acknowledgements

Y.-R.Z. and Z.W acknowledge funding from the Toyota Research Institute. This project has received funding from VILLUM FONDEN (grant no. 9455) and the European Research Council under the European Union’s Horizon 2020 research and innovation programme (grants no. 741860-CLUNATRA, no. 815128−REALNANO and no. 770887−PICOMETRICS). S.B. and S.V.A. acknowledge funding from the Research Foundation Flanders (FWO, G026718N and G050218N). T.A. acknowledges the University of Antwerp Research Fund (BOF). STEM measurements were supported by the European Union’s Horizon 2020 Research Infrastructure-Integrating Activities for Advanced Communities under grant agreement no. 823717 – ESTEEM3.

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  1. These authors contributed equally: Ya-Rong Zheng, Jerome Vernieres, Zhenbin Wang, Ke Zhang.

Authors and Affiliations

  1. Department of Physics, Technical University of Denmark, Kongens Lyngby, Denmark

    Ya-Rong Zheng, Jerome Vernieres, Zhenbin Wang, Ke Zhang, Degenhart Hochfilzer, Kevin Krempl, Ting-Wei Liao, Francesco Presel, Soren Bertelsen Scott, Niklas Mørch Secher, Choongman Moon, Ang Cao, Megha Anand, Jens K. Nørskov, Jakob Kibsgaard & Ib Chorkendorff

  2. Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, China

    Ya-Rong Zheng

  3. Institute of Physics, NAWI Graz, University of Graz, Graz, Austria

    Francesco Presel

  4. EMAT and NANOlab Center of Excellence, University of Antwerp, Antwerp, Belgium

    Thomas Altantzis, Jarmo Fatermans, Pei Liu, Sara Bals & Sandra Van Aert

  5. ELCAT, University of Antwerp, Wilrijk, Belgium

    Thomas Altantzis

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Contributions

I.C., J.K. and J.K.N. conceived and supervised the project. Y.-R.Z. and Z.W co-wrote the manuscript. Y.-R.Z. performed electrochemical tests and collected and analysed the data. J.V., K.Z., T.-W.L., F.P. and N.M.S. performed the mass-selected NP preparation and XPS measurements. Z.W., A.C., M.A. and J.K.N. performed the DFT calculations. K.K., D.H. and S.B.S. assisted in the EC-MS data analysis. T.A., P.L. and S.B. performed the STEM experiments. J.F. and S.V.A. performed the quantitative analysis of the STEM data. C.M. performed the inductively coupled plasma MS measurements. All authors discussed the results and assisted during manuscript preparation.

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Correspondence to Jens K. Nørskov or Ib Chorkendorff.

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Zheng, YR., Vernieres, J., Wang, Z. et al. Monitoring oxygen production on mass-selected iridium–tantalum oxide electrocatalysts. Nat Energy 7, 55–64 (2022). https://doi.org/10.1038/s41560-021-00948-w

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