Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Hydrogen production via microwave-induced water splitting at low temperature

Abstract

Supplying global energy demand with CO2-free technologies is becoming feasible thanks to the rising affordability of renewable resources. Hydrogen is a promising vector in the decarbonization of energy systems, but more efficient and scalable synthesis is required to enable its widespread deployment. Here we report contactless H2 production via water electrolysis mediated by the microwave-triggered redox activation of solid-state ionic materials at low temperatures (<250 °C). Water was reduced via reaction with non-equilibrium gadolinium-doped CeO2 that was previously in situ electrochemically deoxygenated by the sole application of microwaves. The microwave-driven reduction was identified by an instantaneous electrical conductivity rise and O2 release. This process was cyclable, whereas H2 yield and energy efficiency were material- and power-dependent. Deoxygenation of low-energy molecules (H2O or CO2) led to the formation of energy carriers and enabled CH4 production when integrated with a Sabatier reactor. This method could be extended to other reactions such as intensified hydrocarbons synthesis or oxidation.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: Schematic illustration of the microwave-induced redox cycle.
Fig. 2: Microwave radiation process induces reduction of Ce4+ in CeO2.
Fig. 3: Application and time sequence in water deoxygenation.
Fig. 4: Hydrogen production flowchart based on microwave reduction.
Fig. 5: Energy balance and efficiency for hydrogen production.
Fig. 6: Microwave electrocatalysis in energy conversion reactions.

Data availability

The data used in this study are presented in the text, Supplementary Information and Source Data. Additional data and information are available from the corresponding author on request. Source data are provided with this paper.

References

  1. 1.

    Serra, J. M. Electrifying chemistry with protonic cells. Nat. Energy 4, 178–179 (2019).

    Google Scholar 

  2. 2.

    Wei, M., McMillan, C. A. & de la Rue du Can, S. Electrification of industry: potential, challenges and outlook. Curr. Sustain. Energy Rep. 6, 140–148 (2019).

    Google Scholar 

  3. 3.

    Malerød-Fjeld, H. et al. Thermo-electrochemical production of compressed hydrogen from methane with near-zero energy loss. Nat. Energy 2, 923–931 (2017).

  4. 4.

    Schiffer, Z. J. & Manthiram, K. Electrification and decarbonization of the chemical industry. Joule 1, 10–14 (2017).

    Google Scholar 

  5. 5.

    Ran, J., Zhang, J., Yu, J., Jaroniec, M. & Qiao, S. Z. Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. Chem. Soc. Rev. 43, 7787–7812 (2014).

    Google Scholar 

  6. 6.

    Kudo, A. & Miseki, Y. Heterogeneous photocatalyst materials for water splitting. Chem. Soc. Rev. 38, 253–278 (2009).

    Google Scholar 

  7. 7.

    Vøllestad, E. et al. Mixed proton and electron conducting double perovskite anodes for stable and efficient tubular proton ceramic electrolysers. Nat. Mater. 18, 752–759 (2019).

    Google Scholar 

  8. 8.

    Duan, C. et al. Highly efficient reversible protonic ceramic electrochemical cells for power generation and fuel production. Nat. Energy 4, 230–240 (2019).

    Google Scholar 

  9. 9.

    Service, R. F. New electrolyzer splits water on the cheap. Science 367, 1181 (2020).

    Google Scholar 

  10. 10.

    Hamzehlouia, S., Jaffer, S. A. & Chaouki, J. Microwave heating-assisted catalytic dry reforming of methane to syngas. Sci. Rep. 8, 8940 (2018).

    Google Scholar 

  11. 11.

    Tsukahara, Y. et al. In situ observation of nonequilibrium local heating as an origin of special effect of microwave on chemistry. J. Phys. Chem. C 114, 8965–8970 (2010).

    Google Scholar 

  12. 12.

    Sholl, D. S. & Lively, R. P. Seven chemical separations to change the world. Nature 532, 435–437 (2016).

    Google Scholar 

  13. 13.

    Eigen, J. & Schroeder, M. Redox cycling stability of Fe2NiO4/YSZ composite storage materials for rechargeable oxide batteries. Energy Storage Mater. 28, 112–121 (2020).

    Google Scholar 

  14. 14.

    Catalá-Civera, J. M. et al. Dynamic measurement of dielectric properties of materials at high temperature during microwave heating in a dual mode cylindrical cavity. IEEE Trans. Microw. Theory Tech. 63, 2905–2914 (2012).

  15. 15.

    García-Baños, B., Reinosa, J. J., Peñaranda-Foix, F. L., Fernández, J. F. & Catalá-Civera, J. M. Temperature assessment of microwave-enhanced heating processes. Sci. Rep. 9, 10809 (2019).

    Google Scholar 

  16. 16.

    Campbell, C. T. & Peden, C. H. F. Oxygen vacancies and catalysis on ceria surfaces. Science 309, 713–714 (2005).

    Google Scholar 

  17. 17.

    Naghavi, S. S. et al. Giant onsite electronic entropy enhances the performance of ceria for water splitting. Nat. Commun. 8, 1–6 (2017).

    Google Scholar 

  18. 18.

    Chueh, W. C. et al. High-flux solar-driven thermochemical dissociation of CO2 and H2O using nonstoichiometric ceria. Sci. 330, 1797–1801 (2010).

    Google Scholar 

  19. 19.

    Bulfin, B. et al. Analytical model of CeO2 oxidation and reduction. J. Phys. Chem. C 117, 24129–24137 (2013).

    Google Scholar 

  20. 20.

    Geller, A. et al. Operando tracking of electrochemical activity in solid oxide electrochemical cells by using near-infrared imaging. ChemElectroChem 2, 1527–1534 (2015).

    Google Scholar 

  21. 21.

    Balaguer, M., Solís, C. & Serra, J. M. Structural-transport properties relationships on Ce1–xLnxO2–δ system (Ln = Gd, La, Tb, Pr, Eu, Er, Yb, Nd) and effect of cobalt addition. J. Phys. Chem. C 116, 7975–7982 (2012).

    Google Scholar 

  22. 22.

    Holstein, T. Studies of polaron motion. Part II. The ‘small’ polaron. Ann. Phys. (N. Y). 8, 343–389 (1959).

    MATH  Google Scholar 

  23. 23.

    Seki, K. & Tachiya, M. Electric field dependence of charge mobility in energetically disordered materials: polaron aspects. Phys. Rev. B 65, 1–13 (2002).

    Google Scholar 

  24. 24.

    Emin, D. Generalized adiabatic polaron hopping: Meyer–Neldel compensation and Poole–Frenkel behavior. Phys. Rev. Lett. 100, 166602 (2008).

    Google Scholar 

  25. 25.

    Bishop, S. R., Duncan, K. L. & Wachsman, E. D. Surface and bulk oxygen non-stoichiometry and bulk chemical expansion in gadolinium-doped cerium oxide. Acta Mater. 57, 3596–3605 (2009).

    Google Scholar 

  26. 26.

    Suzuki, T., Kosacki, I. & Anderson, H. U. Defect and mixed conductivity in nanocrystalline doped cerium oxide. J. Am. Ceram. Soc. 85, 1492–1498 (2002).

    Google Scholar 

  27. 27.

    Zeng, L., Cheng, Z., Fan, J. A., Fan, L. S. & Gong, J. Metal oxide redox chemistry for chemical looping processes. Nat. Rev. Chem. 2, 349–364 (2018).

    Google Scholar 

  28. 28.

    Liu, W., Song, M.-S., Kong, B. & Cui, Y. Flexible and stretchable energy storage: recent advances and future perspectives. Adv. Mater. 29, 1603436 (2017).

    Google Scholar 

  29. 29.

    Berger, C. M. et al. Development of storage materials for high-temperature rechargeable oxide batteries. J. Energy Storage 1, 54–64 (2015).

    Google Scholar 

  30. 30.

    Posdziech, O., Schwarze, K. & Brabandt, J. Efficient hydrogen production for industry and electricity storage via high-temperature electrolysis. Int. J. Hydrog. Energy 44, 19089–19101 (2019).

    Google Scholar 

  31. 31.

    Maric, R. & Yu, H. In Nanostructures in Energy Generation, Transmission and Storage (IntechOpen, 2018).

  32. 32.

    Dincer, I. & Acar, C. Review and evaluation of hydrogen production methods for better sustainability. Int. J. Hydrog. Energy 40, 11094–11111 (2015).

    Google Scholar 

  33. 33.

    Gielen, D. Hydrogen from Renewable Power Technology Outlook for the Energy Transition (2018).

  34. 34.

    Kuckshinrichs, W., Ketelaer, T. & Koj, J. C. Economic analysis of improved alkaline water electrolysis. Front. Energy Res. 5, 1 (2017).

    Google Scholar 

  35. 35.

    Holladay, J. D., Hu, J., King, D. L. & Wang, Y. An overview of hydrogen production technologies. Catal. Today 139, 244–260 (2009).

    Google Scholar 

  36. 36.

    Glenk, G. & Reichelstein, S. Economics of converting renewable power to hydrogen. Nat. Energy 4, 216–222 (2019).

    Google Scholar 

  37. 37.

    Marxer, D., Furler, P., Takacs, M. & Steinfeld, A. Solar thermochemical splitting of CO2 into separate streams of CO and O2 with high selectivity, stability, conversion, and efficiency. Energy Environ. Sci. 10, 1142–1149 (2017).

    Google Scholar 

  38. 38.

    Vogt, C., Monai, M., Kramer, G. J. & Weckhuysen, B. M. The renaissance of the Sabatier reaction and its applications on Earth and in space. Nat. Catal. 2, 188–197 (2019).

    Google Scholar 

  39. 39.

    Eckle, S., Anfang, H. G. & Behm, R. J. Reaction intermediates and side products in the methanation of CO and CO2 over supported Ru catalysts in H2-rich reformate gases. J. Phys. Chem. C 115, 1361–1367 (2011).

    Google Scholar 

  40. 40.

    Wei, Y. et al. Three-dimensionally ordered macroporous Ce0.8Zr0.2O2-supported gold nanoparticles: synthesis with controllable size and super-catalytic performance for soot oxidation. Energy Environ. Sci. 4, 2959–2970 (2011).

    Google Scholar 

  41. 41.

    Santos, V. P., Pereira, M. F. R., Órfão, J. J. M. & Figueiredo, J. L. The role of lattice oxygen on the activity of manganese oxides towards the oxidation of volatile organic compounds. Appl. Catal. B 99, 353–363 (2010).

    Google Scholar 

  42. 42.

    Hickman, D. A. & Schmidt, L. D. Production of syngas by direct catalytic oxidation of methane. Science 259, 343–346 (1993).

    Google Scholar 

  43. 43.

    Feng, Z. A. et al. Fast vacancy-mediated oxygen ion incorporation across the ceria-gas electrochemical interface. Nat. Commun. 5, 1–9 (2014).

    Google Scholar 

  44. 44.

    Flytzani-Stephanopoulos, M., Sakbodin, M. & Wang, Z. Regenerative adsorption and removal of H2S from hot fuel gas streams by rare earth oxides. Science 312, 1508–1510 (2006).

    Google Scholar 

  45. 45.

    Paunović, V. et al. Europium oxybromide catalysts for efficient bromine looping in natural gas valorization. Angew. Chem. Int. Ed. 56, 9791–9795 (2017).

    Google Scholar 

  46. 46.

    Krupka, J. Contactless methods of conductivity and sheet resistance measurement for semiconductors, conductors and superconductors. Meas. Sci. Technol. 24, 62001 (2013).

    Google Scholar 

  47. 47.

    Altschuler, H. M. Handbook of Microwave Measurements Vol. 2 (Polytechnic Institute Brooklyn Press, 1963).

  48. 48.

    Arai, M., Binner, J. G. P. & Cross, T. E. Comparison of techniques for measuring high-temperature microwave complex permittivity: measurements on an alumina/zircona system. J. Microw. Power Electromagn. Energy 31, 12–18 (1996).

    Google Scholar 

  49. 49.

    López, R. & Gómez, R. Band-gap energy estimation from diffuse reflectance measurements on sol–gel and commercial TiO2: a comparative study. J. Sol.-Gel Sci. Technol. 61, 1–7 (2012).

    Google Scholar 

  50. 50.

    Murphy, A. B. Band-gap determination from diffuse reflectance measurements of semiconductor films, and application to photoelectrochemical water-splitting. Sol. Energy Mater. Sol. Cells 91, 1326–1337 (2007).

    Google Scholar 

  51. 51.

    Skorodumova, N. V. et al. Electronic, bonding, and optical properties of CeO2 and Ce2O3 from first principles. Phys. Rev. B 64, 1151081–1151089 (2001).

    Google Scholar 

Download references

Acknowledgements

This work was supported by the Spanish Government (RTI2018-102161, SEV-2016-0683 and Juan de la Cierva grant IJCI-2017-34110). We thank the support of the Electronic Microscopy Service of the Universitat Politècnica de València.

Author information

Affiliations

Authors

Contributions

J.F.B.-M, P.P.-G., L.N and B.G.-B. performed the experiments. J.M.S., J.M.C.-C., M.B. and B.G.-B. designed the experiments. J.M.C.-C. and P.P.-G designed and fabricated the microwave-cavity assembly. J.F.B.-M, P.P.-G., B.G.-B., J.S.-B., and J.M.C.-C. analysed electrochemical and physical data. M.B, L.N., J.F.B.-M. and J.M.S performed the gas analyses and evaluated catalytic data. D.C.-M. performed thermodynamic and process simulations. M.B. collected physicochemical characterization. J.M.S. and J.M.C.-C. initiated the project. J.M.S., J.M.C.-C., L.N., J.S.-B., D.C.-M. and M.B. wrote the manuscript, whereas all authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to J. M. Serra or J. M. Catalá-Civera.

Ethics declarations

Competing interests

The Universitat Politècnica de València and Consejo Superior de Investigaciones Científicas have jointly applied for a patent based on the method for microwave-driven reduction of oxides and its uses. The inventors are J.M.S., J.F.B.-M., B.G.-B., J.M.C.-C. and L.N and the Spanish priority number is ES2726028-B2.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–23, Notes 1–14, Tables 1–8 and references.

Source data

Source Data Fig. 2

Source data for plots b–d in Fig. 2. Figure 2b displays the flow of oxygen released, in ml min−1, and the CGO material temperature, in °C, as a function of time, in min. Figure 2c compares the electric conductivity behaviour of the solid-state material, in S m−1, for microwave-assisted and conventional heating as a function of inverse temperature, in K−1. Figure 2d reflects an analogous comparison for microwave-assisted heating above and below the material power threshold.

Source Data Fig. 3

Source data for plots b–d in Fig. 3. Figure 3b represents the time sequence, in s, of the control parameters for the microwave-assisted redox process that follows: material absorbed power, in W; temperature, in °C; electric conductivity, in S m−1; and H2 and O2 flows, in ml min−1. Figure 3c compares the time evolution, in s, of the microwave-assisted redox process with H2O and D2O, attending to the following control parameters: temperature, in °C; electric conductivity, in S m−1; and H2 and O2 flows, in arbitrary units. Figure 3d shows the time sequence, in s, of H2 and O2 flows, in ml min−1, and temperature, in °C, for several redox cycles.

Source Data Fig. 6

Source data for plots b and d in Fig. 6. Figure 6b displays the time evolution, in s, of the gas flows involved in CH4 production integrated with a Sabatier reaction, in ml min−1, that is O2, H2, CH4 and CO2. Figure 6d reflects analogous time sequence for the conversion of CH4 into syngas, which involves the gas flows for O2, H2, CH4 and CO, in ml min−1.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Serra, J.M., Borrás-Morell, J.F., García-Baños, B. et al. Hydrogen production via microwave-induced water splitting at low temperature. Nat Energy 5, 910–919 (2020). https://doi.org/10.1038/s41560-020-00720-6

Download citation

Further reading

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing