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.

  • Article
  • Published:

Technical photosynthesis involving CO2 electrolysis and fermentation

Nature Catalysis volume 1, pages 32–39 (2018)Cite this article

Subjects

Abstract

Solar-powered electrochemical reduction of CO2 and H2O to syngas, followed by fermentation, could lead to sustainable production of useful chemicals. However, due to insufficient electric current densities and instabilities of current CO2-to-CO electrolysers, a practical, scalable artificial photosynthesis remains a major challenge. Here, we address these problems using a commercially available silver-based gas diffusion electrode (used in industrial-scale chlorine–alkaline electrolysis) as the cathode in the CO2 electrolyser. Electric current densities up to 300 mA cm–2 were demonstrated for more than 1,200 hours with continuous operation. This CO2 electrolyser was coupled to a fermentation module, where the out-coming syngas from the CO2 electrolyser was converted to butanol and hexanol with high carbon selectivity. Conversion of photovoltaic electricity, CO2 and H2O to the desired alcohols achieved close to 100% Faradaic efficiency. Industrial production of useful and high-value chemicals via artificial photosynthesis is closer than expected with the proposed scalable hybrid system.

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

Access options

Buy this article

  • Purchase on SpringerLink
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Sketch of the modules used in technical photosynthesis of 1-butanol and 1-hexanol from CO2 and H2O.
Fig. 2: Scheme and properties of the CO2 electrolyser.
Fig. 3: Further properties of the CO2 electrolyser shown in Fig. 2a.

Similar content being viewed by others

References

  1. Malveda, M. P., Liu, S., Passararat, S. & Sesto, B. Chemical Economics Handbook: Plasticizer Alcohols (C 4 –C 13 ) 8,86 (IHS Chemical, 2015).

  2. Kim, D., Sakimoto, K. K., Hong, D. C. & Yang, P. D. Artificial photosynthesis for sustainable fuel and chemical production. Angew. Chem. Int. Ed. 54, 3259–3266 (2015).

    Article  CAS  Google Scholar 

  3. Ganesh, I. Solar fuels vis-a-vis electricity generation from sunlight: the current state-of-the-art (a review). Renew. Sust. Energ. Rev. 44, 904–932 (2015).

    Article  CAS  Google Scholar 

  4. Karkas, M. D., Verho, O., Johnston, E. V. & Akermark, B. Artificial photosynthesis: molecular systems for catalytic water oxidation. Chem. Rev. 114, 11863–12001 (2014).

    Article  Google Scholar 

  5. Scott, E. L., Bruins, M. E. & Sanders, J. P. M. Rules for the Bio-Based Production of Bulk Chemicals on a Small Scale: Can the Production of Bulk Chemicals on Small Scale be Competitive? 1–36 (Agrotechnology and Food Science Group, Wageningen UR/Biobased Commodity Chemistry, 2013).

  6. Clomburg, J. M., Crumbley, A. M. & Gonzalez, R. Industrial biomanufacturing: the future of chemical production. Science 355, aag0804 (2017).

    Article  Google Scholar 

  7. Woo, H. M. Solar-to-chemical and solar-to-fuel production from CO2 by metabolically engineered microorganisms. Curr. Opin. Biotechnol. 45, 1–7 (2017).

    Article  CAS  Google Scholar 

  8. Jiao, F. et al. Selective conversion of syngas to light olefins. Science 351, 1065–1068 (2016).

    Article  CAS  Google Scholar 

  9. Polman, A., Knight, M., Garnett, E. C., Ehrler, B. & Sinke, W. C. Photovoltaic materials: present efficiencies and future challenges. Science 352, aad4424 (2016).

    Article  Google Scholar 

  10. Liew, F. et al. Metabolic engineering of Clostridium autoethanogenum for selective alcohol production. Metabol. Eng. 40, 104–114 (2017).

    Article  CAS  Google Scholar 

  11. Mock, J. et al. Energy conservation associated with ethanol formation from H2 and CO2 in Clostridium autoethanogenum involving electron bifurcation. J. Bacteriol. 197, 2965–2980 (2015).

    Article  CAS  Google Scholar 

  12. Dürre, P. Butanol formation from gaseous substrates. FEMS Microbiol. Lett. 363, fnw040 (2016).

    Article  Google Scholar 

  13. von der Assen, N., Muller, L. J., Steingrube, A., Voll, P. & Bardow, A. Selecting CO2 sources for CO2 utilization by environmental-merit-order curves. Environ. Sci. Technol. 50, 1093–1101 (2016).

    Article  Google Scholar 

  14. Hori, Y. & Suzuki, S. Electrolytic reduction of bicarbonate ion at a mercury-electrode. J. Electrochem. Soc. 130, 2387–2390 (1983).

    Article  CAS  Google Scholar 

  15. Asadi, M. et al. Nanostructured transition metal dichalcogenide electrocatalysts for CO2 reduction in ionic liquid. Science 353, 467–470 (2016).

    Article  CAS  Google Scholar 

  16. Gao, S. et al. Partially oxidized atomic cobalt layers for carbon dioxide electroreduction to liquid fuel. Nature 529, 68–71 (2016).

    Article  CAS  Google Scholar 

  17. Neubauer, S. S., Krause, R. K., Schmid, B., Guldi, D. M. & Schmid, G. Overpotentials and Faraday efficiencies in CO2 electrocatalysis-the impact of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate. Adv. Energy Mater. 6, 1502231 (2016).

    Article  Google Scholar 

  18. Verma, S., Lu, X., Ma, S. C., Masel, R. I. & Kenis, P. J. A. The effect of electrolyte composition on the electroreduction of CO2 to CO on Ag-based gas diffusion electrodes. Phys. Chem. Chem. Phys. 18, 7075–7084 (2016).

    Article  CAS  Google Scholar 

  19. Aoi, S., Mase, K., Ohkubo, K. & Fukuzumi, S. Selective electrochemical reduction of CO2 to CO with a cobalt chlorin complex adsorbed on multi-walled carbon nanotubes in water. Chem. Commun. 51, 10226–10228 (2015).

    Article  CAS  Google Scholar 

  20. Kang, P., Chen, Z. F., Brookhart, M. & Meyer, T. J. Electrocatalytic reduction of carbon dioxide: let the molecules do the work. Top. Catal. 58, 30–45 (2015).

    Article  CAS  Google Scholar 

  21. Dufek, E. J., Lister, T. E., Stone, S. G. & McIlwain, M. E. Operation of a pressurized system for continuous reduction of CO2. J. Electrochem. Soc. 159, F514–F517 (2012).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  23. Schreier, M. et al. Solar conversion of CO2 to CO using Earth-abundant electrocatalysts prepared by atomic layer modification of CuO. Nat. Energy 2, 17087 (2017).

    Article  CAS  Google Scholar 

  24. Turek, T., Moussallem, I., Bulan, A., Schmitz, N. & Weuta, P. Oxygen-consuming electrode with multilayer catalytic coating and process for the production thereof. US patent 9,243,337 B2 (2016).

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

    Article  CAS  Google Scholar 

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

    Article  Google Scholar 

  27. Hatsukade, T., Kuhl, K. P., Cave, E. R., Abram, D. N. & Jaramillo, T. F. Insights into the electrocatalytic reduction of CO2 on metallic silver surfaces. Phys. Chem. Chem. Phys. 16, 13814–13819 (2014).

    Article  CAS  Google Scholar 

  28. Mazloomi, K., Sulaiman, N. B. & Moayedi, H. Electrical efficiency of electrolytic hydrogen production. Int. J. Electrochem. Sci. 7, 3314–3326 (2012).

    CAS  Google Scholar 

  29. Liew, F. et al. Gas fermentation: a flexible platform for commercial scale production of low-carbon-fuels and chemicals from waste and renewable feedstocks. Front. Microbiol. 7, 27242719 (2016).

    Article  Google Scholar 

  30. Angenent, L. T. et al. Chain elongation with reactor microbiomes: open-culture biotechnology to produce biochemicals. Environ. Sci. Technol. 50, 2796–2810 (2016).

    Article  CAS  Google Scholar 

  31. Bertsch, J. & Müller, V. Bioenergetic constraints for conversion of syngas to biofuels in acetogenic bacteria. Biotechnol. Biofuels 8, 26692897 (2015).

    Article  Google Scholar 

  32. Wang, S. N. et al. NADP-specific electron-bifurcating [FeFe]-hydrogenase in a functional complex with formate dehydrogenase in Clostridium autoethanogenum grown on CO. J. Bacteriol. 195, 4373–4386 (2013).

    Article  CAS  Google Scholar 

  33. Jones, S. W. et al. CO2 fixation by anaerobic non-photosynthetic mixotrophy for improved carbon conversion. Nat. Commun. 7, 12800 (2016).

    Article  CAS  Google Scholar 

  34. Torella, J. P. et al. Efficient solar-to-fuels production from a hybrid microbial-water-splitting catalyst system. Proc. Natl Acad. Sci. USA 112, 2337–2342 (2015).

    Article  CAS  Google Scholar 

  35. Liu, C., Colon, B. C., Ziesack, M., Silver, P. A. & Nocera, D. G. Water splitting-biosynthetic system with CO2 reduction efficiencies exceeding photosynthesis. Science 352, 1210–1213 (2016).

    Article  CAS  Google Scholar 

  36. Li, H. et al. Integrated electromicrobial conversion of CO2 to higher alcohols. Science 335, 1596–1596 (2012).

    Article  CAS  Google Scholar 

  37. Seedorf, H. et al. The genome of Clostridium kluyveri, a strict anaerobe with unique metabolic features. Proc. Natl Acad. Sci. USA 105, 2128–2133 (2008).

    Article  CAS  Google Scholar 

  38. Li, F. et al. Coupled ferredoxin and crotonyl coenzyme a (CoA) reduction with NADH catalyzed by the butyryl-CoA dehydrogenase/Etf complex from Clostridium kluyveri. J. Bacteriol. 190, 843–850 (2008).

    Article  CAS  Google Scholar 

  39. Perez, J. M., Richter, H., Loftus, S. E. & Angenent, L. T. Biocatalytic reduction of short-chain carboxylic acids into their corresponding alcohols with syngas fermentation. Biotechnol. Bioeng. 110, 1066–1077 (2013).

    Article  CAS  Google Scholar 

  40. Phillips, J. R. et al. Butanol and hexanol production in Clostridium carboxidivorans syngas fermentation: medium development and culture techniques. Bioresource Technol. 190, 114–121 (2015).

    Article  CAS  Google Scholar 

  41. Isom, C. E., Nanny, M. A. & Tanner, R. S. Improved conversion efficiencies for n-fatty acid reduction to primary alcohols by the solventogenic acetogen “Clostridium ragsdalei”. J. Ind. Microbiol. Biotechnol. 42, 29–38 (2015).

    Article  CAS  Google Scholar 

  42. Napora-Wijata, K., Strohmeier, G. A. & Winkler, M. Biocatalytic reduction of carboxylic acids. Biotechnol. J. 9, 822–843 (2014).

    Article  CAS  Google Scholar 

  43. Choi, J. I. & Lee, S. Y. Process analysis and economic evaluation for poly(3-hydroxybutyrate) production by fermentation. Bioprocess. Eng. 17, 335–342 (1997).

    Article  CAS  Google Scholar 

  44. Hermann, T. Industrial production of amino acids by coryneform bacteria. J. Biotechnol. 104, 155–172 (2003).

    Article  CAS  Google Scholar 

  45. Bohlmann, G. M. & Bray, R. Biobutanol Report No. 264 (SRI Consulting, Menlo Park, CA, 2008).

    Google Scholar 

  46. Bohlmann, G. M. & Cesar, M. A. Ethanol Production in Brazil Report No. 149A (SRI Consulting, Menlo Park, CA, 2006).

    Google Scholar 

  47. Bell, S. Bio-Based Succinic Acid (IHS, 2014).

  48. Thauer, R. K., Jungerma., K., Henninge., H., Wenning, J. & Decker, K. Energy metabolism of Clostridium kluyveri. Eur. J. Biochem 4, 173–180 (1968).

    Article  CAS  Google Scholar 

  49. Reports & Markets: Global and Chinese Natural Hexyl Alcohols Report No. CAS 111-27-3 (360 Market Updates, Pune, 2016).

  50. Camara Greiner, E. O., Blagoev, M. & Yamaguchi, Y. Chemical Economics Handbook: Linear Alpha-Olefines (IHS Chemical, 2013).

  51. Schink, B., Kremer, D. R. & Hansen, T. A. Pathway of propionate formation from ethanol in Pelobacter propionicus. Arch. Microbiol. 147, 321–327 (1987).

    Article  CAS  Google Scholar 

  52. Hu, P. et al. Integrated bioprocess for conversion of gaseous substrates to liquids. Proc. Natl Acad. Sci. USA 113, 3773–3778 (2016).

    Article  CAS  Google Scholar 

  53. Li, X., Trevethick, S. & Cossey, B. J. Improved fermentation of gaseous substrates. Patent WO 2015/016722 A1 (2015).

  54. Jörissen, J., Turek, T. & Weber, R. A silver-based oxygen depolarized cathode (ODC). Chemie in unserer Zeit 45, 172–183 (2011).

    Article  Google Scholar 

  55. Dufek, E. J., Lister, T. E. & McIlwain, M. E. Influence of S-contamination on CO2 reduction at Ag electrodes. J. Electrochem. Soc. 158, B1384–B1390 (2011).

    Article  CAS  Google Scholar 

  56. Thauer, R. K., Jungermann, K. & Decker, K. Energy-conservation in chemotropic anaerobic bacteria. Bacteriol. Rev. 41, 100–180 (1977).

    CAS  Google Scholar 

  57. Haegel, N. M. et al. Terawatt-scale photovoltaics: trajectories and challenges. Science 356, 141–143 (2017).

    Article  CAS  Google Scholar 

  58. Xu, G. et al. An improved CO2 separation and purification system based on cryogenic separation and distillation theory. Energies 7, 3484–3502 (2014).

    Article  CAS  Google Scholar 

  59. Service, R. F. Cost of carbon capture drops, but does anyone want it? Science 354, 1362–1363 (2016).

    Article  CAS  Google Scholar 

  60. Diender, M., Stams, A. J. M. & Sousa, D. Z. Production of medium-chain fatty acids and higher alcohols by a synthetic co-culture grown on carbon monoxide or syngas. Biotechnol. Biofuels 9, 27042211 (2016).

    Article  Google Scholar 

Download references

Acknowledgements

The authors thank R. K. Thauer (Max Planck Institute for Terrestrial Microbiology, Marburg) for his help in preparing the manuscript. Evonik Creavis GmbH (T.H. and M.D.), Siemens AG (R.K. and G.S.) and Covestro AG (R.W.) thank the German Federal Ministry of Education and Research (BMBF) for funding part of this work within the Kopernikus Initiative ‘Power-to-X’ under contract number P2X-03SFK2J0.

Author information

Author notes

  1. Ralf Krause and Martin Demler contributed equally to this work.

Authors and Affiliations

  1. Evonik Creavis GmbH, Marl, Germany

    Thomas Haas & Martin Demler

  2. Siemens AG, Erlangen, Germany

    Ralf Krause & Guenter Schmid

  3. Covestro AG, Leverkusen, Germany

    Rainer Weber

Authors
  1. Thomas Haas
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ralf Krause
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rainer Weber
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Martin Demler
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Guenter Schmid
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

G.S. and R.W. discovered the potential of oxygen depolarized cathodes (ODC) for electrochemical CO2-reduction. T.H. and M.D. are responsible for the fermentation part. G.S. and R.K. are responsible for the electrochemical part. M.D. and R.K. performed the laboratory work. G.S. and T.H. are heading the corresponding technology programmes at Siemens AG and Evonik Creavis GmbH, respectively, and wrote the paper.

Corresponding author

Correspondence to Guenter Schmid.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

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. 1–4 and Supplementary Table 1

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Haas, T., Krause, R., Weber, R. et al. Technical photosynthesis involving CO2 electrolysis and fermentation. Nat Catal 1, 32–39 (2018). https://doi.org/10.1038/s41929-017-0005-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41929-017-0005-1

This article is cited by

Search

Advanced 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