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.

Long-term solar water and CO2 splitting with photoelectrochemical BiOI–BiVO4 tandems

Abstract

Photoelectrochemical (PEC) devices have been developed for direct solar fuel production but the limited stability of submerged light absorbers can hamper their commercial prospects.1,2 Here, we demonstrate photocathodes with an operational H2 evolution activity over weeks, by integrating a BiOI light absorber into a robust, oxide-based architecture with a graphite paste conductive encapsulant. In this case, the activity towards proton and CO2 reduction is mainly limited by catalyst degradation. We also introduce multiple-pixel devices as an innovative design principle for PEC systems, displaying superior photocurrents, onset biases and stability over corresponding conventional single-pixel devices. Accordingly, PEC tandem devices comprising multiple-pixel BiOI photocathodes and BiVO4 photoanodes can sustain bias-free water splitting for 240 h, while devices with a Cu92In8 alloy catalyst demonstrate unassisted syngas production from CO2.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: Performance of the individual PV and electrocatalytic components of the BiOI photocathodes.
Fig. 2: Photoelectrochemistry of the BiOI photocathodes.
Fig. 3: PEC performance of the BiOI–BiVO4 tandem devices.

Data availability

The raw data that support the findings of this study are available from the University of Cambridge data repository36: https://doi.org/10.17863/CAM.82399.

References

  1. Kim, J. H., Hansora, D., Sharma, P., Jang, J.-W. & Lee, J. S. Toward practical solar hydrogen production—an artificial photosynthetic leaf-to-farm challenge. Chem. Soc. Rev. 48, 1908–1971 (2019).

  2. Sivula, K. & van de Krol, R. Semiconducting materials for photoelectrochemical energy conversion. Nat. Rev. Mater. 1, 15010 (2016).

    CAS  Article  Google Scholar 

  3. Yan, Q. et al. Solar fuels photoanode materials discovery by integrating high-throughput theory and experiment. Proc. Natl Acad. Sci. USA 114, 3040–3043 (2017).

    CAS  Article  Google Scholar 

  4. Zhou, L. et al. Bi-containing n-FeWO4 thin films provide the largest photovoltage and highest stability for a sub-2 eV band gap photoanode. ACS Energy Lett. 3, 2769–2774 (2018).

    CAS  Article  Google Scholar 

  5. Rettie, A. J. E. et al. Combined charge carrier transport and photoelectrochemical characterization of BiVO4 single crystals: intrinsic behavior of a complex metal oxide. J. Am. Chem. Soc. 135, 11389–11396 (2013).

    CAS  Article  Google Scholar 

  6. Pan, L. et al. Boosting the performance of Cu2O photocathodes for unassisted solar water splitting devices. Nat. Catal. 1, 412–420 (2018).

    CAS  Article  Google Scholar 

  7. Andrei, V., Reuillard, B. & Reisner, E. Bias-free solar syngas production by integrating a molecular cobalt catalyst with perovskite–BiVO4 tandems. Nat. Mater. 19, 189–194 (2020).

  8. Guo, Z. et al. Synthesis of BSA-coated BiOI@Bi2S3 semiconductor heterojunction nanoparticles and their applications for radio/photodynamic/photothermal synergistic therapy of tumor. Adv. Mater. 29, 1704136 (2017).

    Article  Google Scholar 

  9. Mohan, R. Green bismuth. Nat. Chem. 2, 336 (2010).

    CAS  Article  Google Scholar 

  10. Cheng, H., Huang, B. & Dai, Y. Engineering BiOX (X = Cl, Br, I) nanostructures for highly efficient photocatalytic applications. Nanoscale 6, 2009–2026 (2014).

  11. Kim, T. W. & Choi, K.-S. Nanoporous BiVO4 photoanodes with dual-layer oxygen evolution catalysts for solar water splitting. Science 343, 990–994 (2014).

    CAS  Article  Google Scholar 

  12. Hahn, N. T., Hoang, S., Self, J. L. & Mullins, C. B. Spray pyrolysis deposition and photoelectrochemical properties of n-type BiOI nanoplatelet thin films. ACS Nano 6, 7712–7722 (2012).

  13. Bhachu, D. S. et al. Bismuth oxyhalides: synthesis, structure and photoelectrochemical activity. Chem. Sci. 7, 4832–4841 (2016).

    CAS  Article  Google Scholar 

  14. Hoye, R. L. Z. et al. Strongly enhanced photovoltaic performance and defect physics of air-stable bismuth oxyiodide (BiOI). Adv. Mater. 29, 1702176 (2017).

    Article  Google Scholar 

  15. Huq, T. N. et al. Electronic structure and optoelectronic properties of bismuth oxyiodide robust against percent-level iodine-, oxygen-, and bismuth-related surface defects. Adv. Funct. Mater. 30, 1909983 (2020).

    CAS  Article  Google Scholar 

  16. Ganose, A. M., Cu, M., Butler, K. T., Walsh, A. & Scanlon, D. O. Interplay of orbital and relativistic effects in bismuth oxyhalides: BiOF, BiOCl, BiOBr, and BiOI. Chem. Mater. 28, 1980–1984 (2016).

  17. Jagt, R. A. et al. Controlling the preferred orientation of layered BiOI solar absorbers. J. Mater. Chem. C. 102, 10791 (2020).

    Article  Google Scholar 

  18. Nie, W. et al. Light-activated photocurrent degradation and self-healing in perovskite solar cells. Nat. Commun. 7, 11574 (2016).

    CAS  Article  Google Scholar 

  19. Jang, J. et al. Enabling unassisted solar water splitting by iron oxide and silicon. Nat. Commun. 6, 7447 (2015).

    Article  Google Scholar 

  20. Pornrungroj, C. et al. Bifunctional perovskite–BiVO4 tandem devices for uninterrupted solar and electrocatalytic water splitting cycles. Adv. Funct. Mater. 31, 2008182 (2020).

    Article  Google Scholar 

  21. Tilley, S. D., Schreier, M., Azevedo, J., Stefi, M. & Graetzel, M. Ruthenium oxide hydrogen evolution catalysis on composite cuprous oxide water-splitting photocathodes. Adv. Funct. Mater. 24, 303–311 (2014).

  22. Bae, D., Seger, B., Vesborg, P. C. K., Hansen, O. & Chorkendorf, I. Strategies for stable water splitting via protected photoelectrodes. Chem. Soc. Rev. 46, 1933–1954 (2017).

  23. Shen, X. et al. Defect-tolerant TiO2-coated and discretized photoanodes for >600 h of stable photoelectrochemical water oxidation. ACS Energy Lett. 6, 193–200 (2021).

    CAS  Article  Google Scholar 

  24. Burlingame, Q. et al. Intrinsically stable organic solar cells under high-intensity illumination. Nature 573, 394–397 (2019).

    CAS  Article  Google Scholar 

  25. Fakharuddin, A., Rajan, J., Brown, T. M., Fabregat-Santiago, F. & Bisquert, J. A perspective on the production of dye-sensitized solar modules. Energy Environ. Sci. 7, 3952–3981 (2014).

  26. Saliba, M. et al. Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance. Science 354, 206–209 (2016).

    CAS  Article  Google Scholar 

  27. Bai, S. et al. Planar perovskite solar cells with long-term stability using ionic liquid additives. Nature 571, 245–250 (2019).

    CAS  Article  Google Scholar 

  28. Rahaman, M. et al. Selective CO production from aqueous CO2 using a Cu96In4 catalyst and its integration into a bias free solar perovskite–BiVO4 tandem device. Energy Environ. Sci. 13, 3536–3543 (2020).

    CAS  Article  Google Scholar 

  29. Wang, J. et al. Indirect Z-scheme BiOI/g-C3N4 photocatalysts with enhanced photoreduction CO2 activity under visible light irradiation. ACS Appl. Mater. Interfaces 8, 3765–3775 (2016).

    CAS  Article  Google Scholar 

  30. Ye, L. et al. Synthesis of olive-green few-layered BiOI for efficient photoreduction of CO2 into solar fuels under visible/near-infrared light. Sol. Energy Mater. Sol. Cells 144, 732–739 (2016).

    CAS  Article  Google Scholar 

  31. Raninga, R. D. et al. Strong performance enhancement in lead-halide perovskite solar cells through rapid, atmospheric deposition of n-type buffer layer oxides. Nano Energy 75, 104946 (2020).

    CAS  Article  Google Scholar 

  32. Andrei, V., Bethke, K. & Rademann, K. Adjusting the thermoelectric properties of copper(I) oxide–graphite–polymer pastes and the applications of such flexible composites. Phys. Chem. Chem. Phys. 18, 10700–10707 (2016).

  33. Andrei, V. et al. Scalable triple cation mixed halide perovskite–BiVO4 tandems for bias-free water splitting. Adv. Energy Mater. 8, 1801403 (2018).

    Article  Google Scholar 

  34. Lari, L., Lea, S., Feeser, C., Wessels, B. W. & Lazarov, V. K. Ferromagnetic InMnSb multi-phase films study by aberration-corrected (scanning) transmission electron microscopy. J. Appl. Phys. 111, 07C311 (2012).

  35. Harris, D. C. Quantitative Chemical Analysis (W.H. Freeman, 2007).

  36. Andrei, V. et al. Dataset for “Long-term solar water and CO2 splitting with photoelectrochemical BiOI–BiVO4 tandems” (Apollo Repository, Univ. of Cambridge, 2022); https://doi.org/10.17863/CAM.82399

Download references

Acknowledgements

We acknowledge I. Aldawood and A. Althumali for TEM specimen preparation and Z. Sun for aid with BiOI deposition. This work was supported by: the OMV Group (V.A. and E.R.); the Cambridge Trusts (Vice-Chancellor’s Award), the Winton Programme for the Physics of Sustainability, Cambridge Philosophical Society, Trinity College, St John’s College (Title A Research Fellowship; V.A.); an EPSRC Department Training Partnership studentship (EP/N509620/1) and Bill Welland (R.A.J.); a Marie Sklodowska-Curie Individual European Fellowship (SolarFUEL, GAN 839763) and a SNSF EPM Fellowship (P2BEP2_184483; M.R.); the Royal Academy of Engineering under the Research Fellowships scheme (no. RF\201718\1701; R.L.Z.H.); and the Royal Academy of Engineering Chair in Emerging Technologies scheme (no. CIET1819_24; J.L.M.-D.).

Author information

Authors and Affiliations

Authors

Contributions

V.A., R.A.J., R.L.Z.H. and E.R. designed the project. R.A.J. and R.L.Z.H. developed and characterized the BiOI solar cells. V.A. developed the encapsulation, prepared the photoelectrodes and performed the photoelectrochemical characterization. M.R. designed, synthesized and characterized the CO2 reduction catalyst. L.L. and V.K.L. performed TEM characterization and data analysis. V.A. and R.A.J. drafted the manuscript. All authors contributed to the discussion and completion of the manuscript. J.L.M.-D. proposed the use of BiOI for optoelectronic applications. R.L.Z.H. and E.R. supervised the work.

Corresponding authors

Correspondence to Judith L. MacManus-Driscoll, Robert L. Z. Hoye or Erwin Reisner.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Materials thanks the anonymous reviewers for their contribution to the peer review of this work.

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. 1–41, Discussion and Refs. 1–5.

Supplementary Video 1

H2 and syngas production using BiOI photocathodes. Details are given in the embedded video subtitles and in the caption of Supplementary Fig. 41.

Supplementary Video 2

Degradation of unprotected BiOI photocathodes during CVs under chopped light irradiation. Details are given in the video subtitles and in the caption of Supplementary Fig. 15.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Andrei, V., Jagt, R.A., Rahaman, M. et al. Long-term solar water and CO2 splitting with photoelectrochemical BiOI–BiVO4 tandems. Nat. Mater. (2022). https://doi.org/10.1038/s41563-022-01262-w

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/s41563-022-01262-w

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