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Direct magnetic enhancement of electrocatalytic water oxidation in alkaline media

Nature Energy volume 4, pages 519–525 (2019)Cite this article

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Abstract

Industrially profitable water splitting is one of the great challenges in the development of a viable and sustainable hydrogen economy. Alkaline electrolysers using Earth-abundant catalysts remain the most economically viable route to electrolytic hydrogen, but improved efficiency is desirable. Recently, electron spin polarization was described as a potential way to improve water-splitting catalysis. Here, we report the significant enhancement of alkaline water electrolysis when a moderate magnetic field (≤450 mT) is applied to the anode. Current density increments above 100% (over 100 mA cm−2) were found for highly magnetic electrocatalysts, such as the mixed oxide NiZnFe4Ox. Magnetic enhancement works even for decorated Ni–foam electrodes with very high current densities, improving their intrinsic activity by about 40% to reach over 1 A cm−2 at low overpotentials. Thanks to its simplicity, our discovery opens opportunities for implementing magnetic enhancement in water splitting.

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Fig. 1: Magnetic effect on water electrolysis with a bare Ni–foam anode.
Fig. 2: Polarization data under an applied magnetic field for different OER catalysts.
Fig. 3: Magnetic enhancement of water electrolysis under an applied magnetic field.
Fig. 4: Polarization data for surface-modified Ni–foam anodes.

Data availability

All experimental data generated or analysed during this study are included in this published article and its Supplementary Information files.

References

  1. Zhang, B. et al. Homogeneously dispersed multimetal oxygen-evolving catalysts. Science 352, 333–337 (2016).

    Article  Google Scholar 

  2. Xu, Y.-F. et al. In situ formation of zinc ferrite modified Al-doped ZnO nanowire arrays for solar water splitting. J. Mater. Chem. A 4, 5124–5129 (2016).

    Article  Google Scholar 

  3. Cady, C. W. et al. Tuning the electrocatalytic water oxidation properties of AB2O4 spinel nanocrystals: A (Li, Mg, Zn) and B (Mn, Co) site variants of LiMn2O4. ACS Catal. 5, 3403–3410 (2015).

    Article  Google Scholar 

  4. McKone, J. R., Lewis, N. S. & Gray, H. B. Will solar-driven water-splitting devices see the light of day? Chem. Mater. 26, 407–414 (2014).

    Article  Google Scholar 

  5. Schmidt, O., Gambhir, A., Staffell, I., Nelson, J. & Few, S. Future cost and performance of water electrolysis: an expert elicitation study. Int. J. Hydrogen Energy 42, 30470–30492 (2017).

    Article  Google Scholar 

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

    Article  Google Scholar 

  7. Yuan, W., Zhao, M., Yuan, J. & Li, C. M. Ni foam supported three-dimensional vertically aligned and networked layered CoO nanosheet/graphene hybrid array as a high-performance oxygen evolution electrode. J. Power Sources 319, 159–167 (2016).

    Article  Google Scholar 

  8. Jia, J. et al. Solar water splitting by photovoltaic-electrolysis with a solar-to-hydrogen efficiency over 30%. Nat. Commun. 7, 13237 (2016).

    Article  Google Scholar 

  9. Song, F. et al. Transition metal oxides as electrocatalysts for the oxygen evolution reaction in alkaline solutions: an application-inspired renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018).

    Article  Google Scholar 

  10. Guo, C. X. & Li, C. M. Room temperature-formed iron-doped nickel hydroxide on nickel foam as a 3D electrode for low polarized and high-current-density oxygen evolution. Chem. Commun. 54, 3262–3265 (2018).

    Article  Google Scholar 

  11. Trotochaud, L., Young, S. L., Ranney, J. K. & Boettcher, S. W. Nickel–iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation. J. Am. Chem. Soc. 136, 6744–6753 (2014).

    Article  Google Scholar 

  12. Zeng, K. & Zhang, D. Recent progress in alkaline water electrolysis for hydrogen production and applications. Prog. Energy Combust. Sci. 36, 307–326 (2010).

    Article  Google Scholar 

  13. McCrory, C. C. L., Jung, S., Peters, J. C. & Jaramillo, T. F. Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J. Am. Chem. Soc. 4, 16977–16987 (2013).

    Article  Google Scholar 

  14. Gracia, J. Spin dependent interactions catalyse the oxygen electrochemistry. Phys. Chem. Chem. Phys. 19, 20451–20456 (2017).

    Article  Google Scholar 

  15. Gracia, J., Sharpe, R. & Munarriz, J. Principles determining the activity of magnetic oxides for electron transfer reactions. J. Catal. 361, 331–338 (2018).

    Article  Google Scholar 

  16. Mtangi, W., Kiran, V., Fontanesi, C. & Naaman, R. Role of the electron spin polarization in water splitting. J. Phys. Chem. Lett. 6, 4916–4922 (2015).

    Article  Google Scholar 

  17. Mtangi, W. et al. Control of electrons’ spin eliminates hydrogen peroxide formation during water splitting. J. Am. Chem. Soc. 139, 2794–2798 (2017).

    Article  Google Scholar 

  18. Zhang, W., Banerjee-Ghosh, K., Tassanari, F. & Naaman, R. Enhanced electrochemical water splitting with chiral molecule-coated Fe3O4 nanoparticles. ACS Energy Lett. 3, 2308–2313 (2018).

    Article  Google Scholar 

  19. Chretien, S. & Metiu, H. O2 evolution on a clean partially reduced rutile TiO2 (110) surface and on the same surface precovered with Au1 and Au2: the importance of spin conservation. J. Chem. Phys. 129, 074705 (2008).

    Article  Google Scholar 

  20. Torum, E., Fang, C. M., de Wijs, G. A. & de Groot, R. A. Role of magnetism in catalysis: RuO2 (110) surface. J. Phys. Chem. C 117, 6353–6357 (2013).

    Article  Google Scholar 

  21. Jiao, J., Sharpe, R., Lim, T., Niemantsverdriett, J. W. H. & Gracia, J. Photosystem II acts as a spin-controlled electron gate during oxygen formation and evolution. J. Am. Chem. Soc. 139, 16604–16608 (2017).

    Article  Google Scholar 

  22. Elias, L. & Hegde, C. Effect of magnetic field on HER of water electrolysis on NiÐW alloy. Electrocatalysis 8, 375–382 (2017).

    Article  Google Scholar 

  23. Zheng, Z. et al. Magnetic field-enhanced 4-electron pathway for well-aligned Co3O4/electrospun carbon nanofibers in the oxygen reduction reaction. Chem. Sus. Chem. 11, 580–588 (2018).

    Article  Google Scholar 

  24. Katz, E., Lioubashevski, O. & Willner, I. Magnetic field effects on bioelectrocatalytic reactions of surface-confined enzyme systems: enhanced performance of biofuel cells. J. Am. Chem. Soc. 127, 3979–3988 (2005).

    Article  Google Scholar 

  25. Monzon, L. M. A., Rode, K., Venkatesan, M. & Coey, J. Electrosynthesis of iron, cobalt, and zinc microcrystals and magnetic enhancement of the oxygen reduction reaction. Chem. Mater. 24, 3878–3885 (2012).

    Article  Google Scholar 

  26. Niether, C. et al. Improved water electrolysis using magnetic heating of FeC–Ni core–shell nanoparticles. Nat. Energy 3, 476–483 (2018).

    Article  Google Scholar 

  27. Giordano, L. et al. pH dependence of OER activity of oxides: current and future perspectives. Catal. Today 262, 2–10 (2016).

    Article  Google Scholar 

  28. McCrory, C. C. L. et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am. Chem. Soc. 137, 4347–4357 (2015).

    Article  Google Scholar 

  29. Trotochaud, L., Ranney, J. K., Williams, K. N. & Boettcher, S. W. Solution-cast metal oxide thin film electrocatalysts for oxygen evolution. J. Am. Chem. Soc. 134, 17253–17261 (2012).

    Article  Google Scholar 

  30. Gerken, J. B., Shaner, S. E., Massé, R. C., Porubsky, N. J. & Stahl, S. S. A survey of diverse Earth abundant oxygen evolution electrocatalysts showing enhanced activity from Ni–Fe oxides containing a third metal. Energy Environ. Sci. 7, 2376–2382 (2014).

    Article  Google Scholar 

  31. Smith, R. D. L. et al. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis. Science 340, 60–63 (2013).

    Article  Google Scholar 

  32. 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 

  33. Liu, G., Wang, K., Gao, X., He, D. & Li, J. Fabrication of mesoporous NiFe2O4 nanorods as efficient oxygen evolution catalyst for water splitting. Electrochim. Acta 211, 871–878 (2016).

    Article  Google Scholar 

  34. Liu, G., Gao, X., Wang, K., He, D. & Li, J. Uniformly mesoporous NiO/NiFe2O4 biphasic nanorods as efficient oxygen evolving catalyst for water splitting. Int. J. Hydrogen Energy 41, 17976–17986 (2016).

    Article  Google Scholar 

  35. Dez-Garca, M. I., Lana-Villarreal, T. & Gómez, R. Study of copper ferrite as a novel photocathode for water reduction: improving its photoactivity by electrochemical pretreatment. ChemSusChem 9, 1504–1512 (2016).

    Article  Google Scholar 

  36. Ng, J. W. D. et al. Gold-supported cerium-doped NiOx catalysts for water oxidation. Nat. Energy 1, 16053 (2016).

    Article  Google Scholar 

  37. Islam, M. U. et al. Electrical behaviour of fine particle, co-precipitation prepared Ni–Zn ferrites. Solid State Commun. 130, 353–356 (2004).

    Article  Google Scholar 

  38. Wang, X. et al. A novel NiZn ferrite integrated magnetic solenoid inductor with a high quality factor at 0.7–6 GHz. AIP Adv. 7, 056606 (2017).

    Article  Google Scholar 

  39. He, Q. et al. Electrically controllable spontaneous magnetism in nanoscale mixed phase multiferroics. Nat. Commun. 2, 225 (2011).

    Article  Google Scholar 

  40. Su, Y.-Z. et al. One dimensionally spinel NiCo2O4 nanowire arrays: facile synthesis, water oxidation, and magnetic properties. Electrochim. Acta 174, 1216–1224 (2015).

    Article  Google Scholar 

  41. Mayrhofer, K. J. J., Wiberg, G. K. H. & Arenz, M. Impact of glass corrosion on the electrocatalysis on Pt electrodes in alkaline electrolyte. J. Electrochem. Soc. 155, P1–P5 (2008).

    Article  Google Scholar 

  42. Rodriguez, P., Tichelaar, F. D., Koper, M. T. M. & Yanson, A. I. Cathodic corrosion as a facile and effective method to prepare clean metal alloy nanoparticles. J. Am. Chem. Soc. 133, 17626–17629 (2011).

    Article  Google Scholar 

  43. Chen, R. et al. Use of platinum as the counter electrode to study the activity of nonprecious metal catalysts for the hydrogen evolution reaction. ACS Energy Lett. 2, 1070–1075 (2017).

    Article  Google Scholar 

  44. Dong, G. et al. In situ formation of highly active NiFe based oxygen-evolving electrocatalysts via simple reactive dip-coating. J. Mater. Chem. A 5, 11009–11015 (2017).

    Article  Google Scholar 

  45. Zhou, H. et al. Highly active catalyst derived from a 3D foam of Fe(PO3)2/Ni2P for extremely efficient water oxidation. Proc. Natl Acad. Sci. USA 114, 5607–5611 (2017).

    Article  Google Scholar 

  46. Chen, J. Y. C., Miller, J. T., Gerken, J. B. & Stahl, S. S. Inverse spinel NiFeAlO4 as a highly active oxygen evolution electrocatalyst: promotion of activity by a redox-inert metal ion. Energy Environ. Sci. 7, 1382–1386 (2014).

    Article  Google Scholar 

  47. Carmo, M., Doubek, G., Sekol, R. C., Linardi, M. & Taylor, A. D. Development and electrochemical studies of membrane electrode assemblies for polymer electrolyte alkaline fuel cells using FAA membrane and ionomer. J. Power Sources 230, 169–175 (2013).

    Article  Google Scholar 

  48. Ellms, J. W. & Hauser, S. J. Ortho-tolidine as a reagent for the colorimetric estimation of small quantities of free chlorine. J. Ind. Eng. Chem. 5, 915–917 (1913).

    Article  Google Scholar 

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Acknowledgements

This work was funded by: the European Union’s Horizon 2020 research and innovation programme under grant agreement CREATE number 721065; FEDER/Ministerio de Ciencia, Innovación y Universidades – Agencia Estatal de Investigación/RTI2018-095618-B-I0; and the Generalitat de Catalunya (2017-SGR-1406 and the CERCA Programme). The authors also acknowledge BSC-RES for computational resources.

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Authors and Affiliations

  1. Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona, Spain

    Felipe A. Garcés-Pineda, Marta Blasco-Ahicart, David Nieto-Castro, Núria López & José Ramón Galán-Mascarós

  2. Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain

    José Ramón Galán-Mascarós

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Contributions

J.R.G.-M. and N.L. proposed the concept. F.A.G.-P. and J.R.G.-M. designed the experiments. M.B.-A. and F.A.G.-P. performed the synthesis, processing and electrochemical experiments. D.N.-C. performed the magnetic measurements and analyses. N.L. performed the computational studies. All authors wrote the manuscript.

Corresponding author

Correspondence to José Ramón Galán-Mascarós.

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The authors declare no competing interests.

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Supplementary information

Supplementary Information

Supplementary methods, discussion, Figs. 1–18, Tables 1 and 2, and references

Supplementary Video 1

Water electrolysis enhancement on approaching a permanent magnet to a Ni–foam/NiZnFe4Ox-decorated anode working at a constant voltage of 1.67 V versus RHE in a single cell.

Supplementary Video 2

Water electrolysis enhancement on approaching a permanent magnet to a Ni–foam/NiZnFeOx-decorated anode working at 100 mA cm−2 in a single cell.

Supplementary Video 3

Anodic current enhancement on approaching a permanent magnet to a Ni–foam/NiZnFeOx-decorated anode working at 10 mA cm−2 in a H cell.

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Garcés-Pineda, F.A., Blasco-Ahicart, M., Nieto-Castro, D. et al. Direct magnetic enhancement of electrocatalytic water oxidation in alkaline media. Nat Energy 4, 519–525 (2019). https://doi.org/10.1038/s41560-019-0404-4

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