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.

Bias-free solar syngas production by integrating a molecular cobalt catalyst with perovskite–BiVO4 tandems

Abstract

The photoelectrochemical (PEC) production of syngas from water and CO2 represents an attractive technology towards a circular carbon economy. However, the high overpotential, low selectivity and cost of commonly employed catalysts pose challenges for this sustainable energy-conversion process. Here we demonstrate highly tunable PEC syngas production by integrating a cobalt porphyrin catalyst immobilized on carbon nanotubes with triple-cation mixed halide perovskite and BiVO4 photoabsorbers. Empirical data analysis is used to clarify the optimal electrode selectivity at low catalyst loadings. The perovskite photocathodes maintain selective aqueous CO2 reduction for one day at light intensities as low as 0.1 sun, which provides pathways to maximize daylight utilization by operating even under low solar irradiance. Under 1 sun irradiation, the perovskite–BiVO4 PEC tandems sustain bias-free syngas production coupled to water oxidation for three days. The devices present solar-to-H2 and solar-to-CO conversion efficiencies of 0.06 and 0.02%, respectively, and are able to operate as standalone artificial leaves in neutral pH solution.

This is a preview of subscription content, access via your institution

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Fig. 1: Architecture of the standalone perovskite–BiVO4 PEC tandem device for bias-free syngas production.
Fig. 2: Electrocatalysis of CoMTPP@CNT electrodes.
Fig. 3: PEC performance of the perovskite|CoMTPP@CNT photocathode.
Fig. 4: PEC of the BiVO4–perovskite|CoMTPP@CNT tandem device.

Data availability

The raw data that support the findings of this study are available from the University of Cambridge data repository53: https://doi.org/10.17863/CAM.44164.

References

  1. Behrens, M. et al. The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts. Science 336, 893–897 (2012).

    CAS  Google Scholar 

  2. Khodakov, A. Y., Chu, W. & Fongarland, P. Advances in the development of novel cobalt Fischer–Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels. Chem. Rev. 107, 1692–1744 (2007).

    CAS  Google Scholar 

  3. Bharadwaj, S. S. & Schmidt, L. D. Catalytic partial oxidation of natural gas to syngas. Fuel Process. Technol. 42, 109–127 (1995).

    CAS  Google Scholar 

  4. Abdoulmoumine, N., Adhikari, S., Kulkarni, A. & Chattanathan, S. A review on biomass gasification syngas cleanup. Appl. Energy 155, 294–307 (2015).

    CAS  Google Scholar 

  5. Graves, C., Ebbesen, S. D., Mogensen, M. & Lackner, K. S. Sustainable hydrocarbon fuels by recycling CO2 and H2O with renewable or nuclear energy. Renew. Sustain. Energy Rev. 15, 1–23 (2011).

    CAS  Google Scholar 

  6. Shaner, M. R. et al. Photoelectrochemistry of core–shell tandem junction n–p+-Si/n-WO3 microwire array photoelectrodes. Energy Environ. Sci. 7, 779–790 (2014).

    CAS  Google Scholar 

  7. Brillet, J. et al. Highly efficient water splitting by a dual-absorber tandem cell. Nat. Photon. 6, 824 (2012).

    CAS  Google Scholar 

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

    CAS  Google Scholar 

  9. Wang, Q. et al. Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%. Nat. Mater. 15, 611 (2016).

    CAS  Google Scholar 

  10. Lu, H. et al. Single-source bismuth (transition metal) polyoxovanadate precursors for the scalable synthesis of doped BiVO4 photoanodes. Adv. Mater. 30, 1804033 (2018).

    Google Scholar 

  11. Luo, J. et al. Water photolysis at 12.3% efficiency via perovskite photovoltaics and earth-abundant catalysts. Science 345, 1593–1596 (2014).

    CAS  Google Scholar 

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

    Google Scholar 

  13. Schreier, M. et al. Efficient photosynthesis of carbon monoxide from CO2 using perovskite photovoltaics. Nat. Commun. 6, 7326 (2015).

    CAS  Google Scholar 

  14. Jang, Y. J. et al. Unbiased sunlight-driven artificial photosynthesis of carbon monoxide from CO2 using a ZnTe-based photocathode and a perovskite solar cell in tandem. ACS Nano 10, 6980–6987 (2016).

    CAS  Google Scholar 

  15. Sokol, K. P. et al. Photoreduction of CO2 with a formate dehydrogenase driven by photosystem II using a semi-artificial Z-scheme architecture. J. Am. Chem. Soc. 140, 16418–16422 (2018).

    CAS  Google Scholar 

  16. Li, C. et al. Photoelectrochemical CO2 reduction to adjustable syngas on grain-boundary-mediated a-Si/TiO2/Au photocathodes with low onset potentials. Energy Environ. Sci. 12, 923–928 (2019).

    CAS  Google Scholar 

  17. Sahara, G. et al. Photoelectrochemical reduction of CO2 coupled to water oxidation using a photocathode with a Ru(ii)–Re(i) complex photocatalyst and a CoOx/TaON photoanode. J. Am. Chem. Soc. 138, 14152–14158 (2016).

    CAS  Google Scholar 

  18. Urbain, F. et al. A prototype reactor for highly selective solar-driven CO2 reduction to synthesis gas using nanosized earth-abundant catalysts and silicon photovoltaics. Energy Environ. Sci. 10, 2256–2266 (2017).

    CAS  Google Scholar 

  19. Arai, T., Sato, S., Sekizawa, K., Suzuki, T. M. & Morikawa, T. Solar-driven CO2 to CO reduction utilizing H2O as an electron donor by earth-abundant Mn–bipyridine complex and Ni-modified Fe-oxyhydroxide catalysts activated in a single-compartment reactor. Chem. Commun. 55, 237–240 (2019).

    CAS  Google Scholar 

  20. Voiry, D., Shin, H. S., Loh, K. P. & Chhowalla, M. Low-dimensional catalysts for hydrogen evolution and CO2 reduction. Nat. Rev. Chem. 2, 0105 (2018).

    CAS  Google Scholar 

  21. Francke, R., Schille, B. & Roemelt, M. Homogeneously catalyzed electroreduction of carbon dioxide—methods, mechanisms, and catalysts. Chem. Rev. 118, 4631–4701 (2018).

    CAS  Google Scholar 

  22. Dalle, K. E. et al. Electro- and solar-driven fuel synthesis with first row transition metal complexes. Chem. Rev. 119, 2752–2875 (2019).

    CAS  Google Scholar 

  23. Costentin, C., Drouet, S., Robert, M. & Savéant, J.-M. A local proton source enhances CO2 electroreduction to CO by a molecular Fe catalyst. Science 338, 90–94 (2012).

    CAS  Google Scholar 

  24. Lin, S. et al. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 349, 1208–1213 (2015).

    CAS  Google Scholar 

  25. Zhu, M., Ye, R., Jin, K., Lazouski, N. & Manthiram, K. Elucidating the reactivity and mechanism of CO2 electroreduction at highly dispersed cobalt phthalocyanine. ACS Energy Lett. 3, 1381–1386 (2018).

    CAS  Google Scholar 

  26. Hu, X.-M., Rønne, M. H., Pedersen, S. U., Skrydstrup, T. & Daasbjerg, K. Enhanced catalytic activity of cobalt porphyrin in CO2 electroreduction upon immobilization on carbon materials. Angew. Chem. Int. Ed. 56, 6468–6472 (2017).

    CAS  Google Scholar 

  27. Zhang, X. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 8, 14675 (2017).

    Google Scholar 

  28. Li, C. W., Ciston, J. & Kanan, M. W. Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper. Nature 508, 504–507 (2014).

    CAS  Google Scholar 

  29. Hall, A. S., Yoon, Y., Wuttig, A. & Surendranath, Y. Mesostructure-induced selectivity in CO2 reduction catalysis. J. Am. Chem. Soc. 137, 14834–14837 (2015).

    CAS  Google Scholar 

  30. Ma, M., Trześniewski, B. J., Xie, J. & Smith, W. A. Selective and efficient reduction of carbon dioxide to carbon monoxide on oxide-derived nanostructured silver electrocatalysts. Angew. Chem. Int. Ed. 55, 9748–9752 (2016).

    CAS  Google Scholar 

  31. de Luna, P. et al. Catalyst electro-redeposition controls morphology and oxidation state for selective carbon dioxide reduction. Nat. Catal. 1, 103–110 (2018).

    Google Scholar 

  32. Suter, S. & Haussener, S. Optimizing mesostructured silver catalysts for selective carbon dioxide conversion into fuels. Energy Environ. Sci. 12, 1668–1678 (2019).

    CAS  Google Scholar 

  33. Sharma, A. & Kakkar, A. Forecasting daily global solar irradiance generation using machine learning. Renew. Sustain. Energy Rev. 82, 2254–2269 (2018).

    Google Scholar 

  34. Stoffel, T. & Andreas, A. NREL Solar Radiation Research Laboratory (SRRL): Baseline Measurement System (BMS); Golden, Colorado (Data) NREL Report no. DA-5500-56488(NREL, 1981).

  35. Hernández-Pagán, E. A. et al. Resistance and polarization losses in aqueous buffer–membrane electrolytes for water-splitting photoelectrochemical cells. Energy Environ. Sci. 5, 7582–7589 (2012).

    Google Scholar 

  36. Vermaas, D. A. & Smith, W. A. Synergistic electrochemical CO2 reduction and water oxidation with a bipolar membrane. ACS Energy Lett. 1, 1143–1148 (2016).

    CAS  Google Scholar 

  37. Singh, M. R., Xiang, C. & Lewis, N. S. Evaluation of flow schemes for near-neutral pH electrolytes in solar-fuel generators. Sustain. Energy Fuels 1, 458–466 (2017).

    CAS  Google Scholar 

  38. 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).

    CAS  Google Scholar 

  39. Lee, Y. W. et al. Unbiased biocatalytic solar-to-chemical conversion by FeOOH/BiVO4/perovskite tandem structure. Nat. Commun. 9, 4208 (2018).

    Google Scholar 

  40. Zhang, H. et al. A sandwich-like organolead halide perovskite photocathode for efficient and durable photoelectrochemical hydrogen evolution in water. Adv. Energy Mater. 8, 1800795 (2018).

    Google Scholar 

  41. Joya, K. S., Joya, Y. F., Ocakoglu, K. & van de Krol, R. Water-splitting catalysis and solar fuel devices: artificial leaves on the move. Angew. Chem. Int. Ed. 52, 10426–10437 (2013).

    CAS  Google Scholar 

  42. Hu, S., Xiang, C., Haussener, S., Berger, A. D. & Lewis, N. S. An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical water-splitting systems. Energy Environ. Sci. 6, 2984–2993 (2013).

    CAS  Google Scholar 

  43. Wang, Q., Dong, Q., Li, T., Gruverman, A. & Huang, J. Thin insulating tunneling contacts for efficient and water-resistant perovskite solar cells. Adv. Mater. 28, 6734–6739 (2016).

    CAS  Google Scholar 

  44. Qiu, Y. et al. Efficient solar-driven water splitting by nanocone BiVO4–perovskite tandem cells. Sci. Adv. 2, e1501764 (2016).

    Google Scholar 

  45. Azcarate, I., Costentin, C., Robert, M. & Savéant, J.-M. Through-space charge interaction substituent effects in molecular catalysis leading to the design of the most efficient catalyst of CO2-to-CO electrochemical conversion. J. Am. Chem. Soc. 138, 16639–16644 (2016).

    CAS  Google Scholar 

  46. Sato, S., Saita, K., Sekizawa, K., Maeda, S. & Morikawa, T. Low-energy electrocatalytic CO2 reduction in water over Mn–complex catalyst electrode aided by a nanocarbon support and K+ cations. ACS Catal. 8, 4452–4458 (2018).

    CAS  Google Scholar 

  47. Zhou, X. et al. Solar-driven reduction of 1 atm of CO2 to formate at 10% energy-conversion efficiency by use of a TiO2-protected III–V tandem photoanode in conjunction with a bipolar membrane and a Pd/C cathode. ACS Energy Lett. 1, 764–770 (2016).

    CAS  Google Scholar 

  48. Reece, S. Y. et al. Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts. Science 334, 645–648 (2011).

    CAS  Google Scholar 

  49. Rao, H., Schmidt, L. C., Bonin, J. & Robert, M. Visible-light-driven methane formation from CO2 with a molecular iron catalyst. Nature 548, 74 (2017).

    CAS  Google Scholar 

  50. Reuillard, B., Warnan, J., Leung, J. J., Wakerley, D. W. & Reisner, E. A poly(cobaloxime)/carbon nanotube electrode: freestanding buckypaper with polymer-enhanced H2-evolution performance. Angew. Chem. Int. Ed. 55, 3952–3957 (2016).

    CAS  Google Scholar 

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

    Google Scholar 

  52. Harris, D. C. Quantitative Chemical Analysis 7th edn. (W.H. Freeman and Co., New York, NY, 2007).

  53. Andrei, V., Reuillard, B. & Reisner, E. Raw Data Supporting Article: Bias-free Solar Syngas Production by Integrating a Molecular Cobalt Catalyst with Perovskite–BiVO 4 Tandems (2019); https://doi.org/10.17863/CAM.44164

Download references

Acknowledgements

This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry for Digital and Economic Affairs and the National Foundation for Research, Technology and Development) and the OMV Group (E.R.). V.A. is grateful for the financial support from the Cambridge Trusts (Vice-Chancellor’s Award) and the Winton Programme for the Physics of Sustainability. B.R. was supported by the BBSRC (grant no. BB/K010220/1). XPS data collection was performed at the EPSRC National Facility for Photoelectron spectroscopy (‘HarwellXPS’), operated by Cardiff University and UCL under contract no. PR16195. We acknowledge D. S. Wright (University of Cambridge) for providing us the Co WOC precursor. We thank A. Dickerson (University of Cambridge) for the ICP-OES measurements. We are grateful to D. Achilleos (University of Cambridge) for help with XPS sample preparation and data analysis. We thank K. P. Sokol (University of Cambridge) for helpful advice on the O2 measurements, and K. P. Sokol and A. Wagner (University of Cambridge) for useful feedback on the manuscript.

Author information

Authors and Affiliations

Authors

Contributions

V.A., B.R. and E.R. designed the project. V.A. prepared the photoelectrodes, performed the experiments and drafted the manuscript. V.A., B.R. and E.R. analysed the data. B.R. and E.R. contributed to the discussion and completion of the manuscript. E.R. supervised the work.

Corresponding author

Correspondence to Erwin Reisner.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

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

Supplementary information

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

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). https://doi.org/10.1038/s41563-019-0501-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41563-019-0501-6

This article is cited by

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