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:

Solar-driven reforming of lignocellulose to H2 with a CdS/CdOx photocatalyst

Nature Energy volume 2, Article number: 17021 (2017) Cite this article

Subjects

Abstract

Lignocellulose is Earth’s most abundant form of biomass and its valorization to H2 is a key objective for the generation of renewable fuels. Solar-driven photocatalytic reforming of lignocellulose to H2 at ambient temperature offers a sustainable route towards this goal, but this reaction is currently limited to noble-metal-containing systems that operate with low activity under ultraviolet light. Here, we report the light-driven photoreforming of cellulose, hemicellulose and lignin to H2 using semiconducting cadmium sulfide quantum dots in alkaline aqueous solution. We show that basic conditions cause these dots to become coated with oxide/hydroxide in situ, presenting a strategy to improve their photocatalytic performance. The system operates under visible light, is stable beyond six days and is even able to reform unprocessed lignocellulose, such as wood and paper, under solar irradiation at room temperature, presenting an inexpensive route to drive aqueous proton reduction to H2 through waste biomass oxidation.

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

Figure 1: Photoreforming of lignocellulose to H2 on CdS/CdOx.
Figure 2: Characterization of CdS/CdOx.
Figure 3: Photoreforming of cellulose to H2 using CdS/CdOx.
Figure 4: The rate of H2 generation through photoreforming lignocellulose on CdS/CdOx.

Similar content being viewed by others

References

  1. US Energy Information Administration Short-Term Energy and Summer Fuels Outlook (US Department of Energy, 2016).

  2. Tertzakian, P. A Thousand Barrels a Second: The Coming Oil Break Point and the Challenges Facing an Energy Dependent World (McGraw-Hill Education, 2006).

    Google Scholar 

  3. Murray, J. & King, D. Oil’s tipping point has passed. Nature 481, 433–435 (2012).

    Google Scholar 

  4. IPCC Climate Change 2013: The Physical Science Basis (eds Stocker, T. F. et al.) (Cambridge Univ. Press, 2013).

    Google Scholar 

  5. Tracking Clean Energy Progress 2015—Energy Technology Perspectives 2015 Excerpt IEA Input to the Clean Energy Ministerial (International Energy Agency, 2015).

  6. Moret, S., Dyson, P. J. & Laurenczy, G. Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media. Nat. Commun. 5, 4017 (2014).

    Google Scholar 

  7. Iulianelli, A., Liguori, S., Wilcox, J. & Basile, A. Advances on methane steam reforming to produce hydrogen through membrane reactors technology: a review. Catal. Rev. 58, 1–35 (2016).

    Google Scholar 

  8. US Department of Energy Multi-Year Research, Development, and Demonstration Plan—3.1 Hydrogen Production (Office of Energy Efficiency Renewable Energy, 2015).

  9. Rubin, E. M. Genomics of cellulosic biofuels. Nature 454, 841–845 (2008).

    Google Scholar 

  10. Huber, G. W., Iborra, S. & Corma, A. Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. Chem. Rev. 106, 4044–4098 (2006).

    Google Scholar 

  11. Zinoviev, S. et al. Next-generation biofuels: survey of emerging technologies and sustainability issues. ChemSusChem 3, 1106–1133 (2010).

    Google Scholar 

  12. Puga, A. V. Photocatalytic production of hydrogen from biomass-derived feedstocks. Coord. Chem. Rev. 315, 1–66 (2016).

    Google Scholar 

  13. Shimura, K. & Yoshida, H. Heterogeneous photocatalytic hydrogen production from water and biomass derivatives. Energy Environ. Sci. 4, 2467–2481 (2011).

    Google Scholar 

  14. Xia, Q. et al. Direct hydrodeoxygenation of raw woody biomass into liquid alkanes. Nat. Commun. 7, 11162 (2016).

    Google Scholar 

  15. Li, C., Zheng, M., Wang, A. & Zhang, T. One-pot catalytic hydrocracking of raw woody biomass into chemicals over supported carbide catalysts: simultaneous conversion of cellulose, hemicellulose and lignin. Energy Environ. Sci. 5, 6383–6390 (2012).

    Google Scholar 

  16. Himmel, M. E. et al. Biomass recalcitrance: engineering plants and enzymes for biofuels production. Science 315, 804–807 (2007).

    Google Scholar 

  17. Sun, Y. & Cheng, J. Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresour. Technol. 83, 1–11 (2002).

    Google Scholar 

  18. Zhang, G. et al. Simultaneous cellulose conversion and hydrogen production assisted by cellulose decomposition under UV-light photocatalysis. Chem. Commun. 52, 1673–1676 (2016).

    Google Scholar 

  19. Kawai, T. & Sakata, T. Conversion of carbohydrate into hydrogen fuel by a photocatalytic process. Nature 286, 474–476 (1980).

    Google Scholar 

  20. Speltini, A. et al. Sunlight-promoted photocatalytic hydrogen gas evolution from water-suspended cellulose: a systematic study. Photochem. Photobiol. Sci. 13, 1410–1419 (2014).

    Google Scholar 

  21. Xu, Y. & Schoonen, M. A. A. The absolute energy positions of conduction and valence bands of selected semiconducting minerals. Am. Mineral. 85, 543–556 (2000).

    Google Scholar 

  22. Cao, S., Chen, Y., Wang, C.-J., Lv, X.-J. & Fu, W.-F. Spectacular photocatalytic hydrogen evolution using metal-phosphide/CdS hybrid catalysts under sunlight irradiation. Chem. Commun. 51, 8708–8711 (2015).

    Google Scholar 

  23. Xu, Y., Huang, Y. & Zhang, B. Rational design of semiconductor-based photocatalysts for advanced photocatalytic hydrogen production: the case of cadmium chalcogenides. Inorg. Chem. Front. 3, 591–615 (2016).

    Google Scholar 

  24. Budtova, T. & Navard, P. Cellulose in NaOH-water based solvents: a review. Cellulose 23, 5–55 (2016).

    Google Scholar 

  25. Chang, C. M., Orchard, K. L., Martindale, B. C. M. & Reisner, E. Ligand removal from CdS quantum dots for enhanced photocatalytic H2 generation in pH neutral water. J. Mater. Chem. A 4, 2856–2862 (2016).

    Google Scholar 

  26. Spanhel, L., Haase, M., Weller, H. & Henglein, A. Photochemistry of colloidal semiconductors. 20. Surface modification and stability of strong luminescing CdS particles. J. Am. Chem. Soc. 109, 5649–5655 (1987).

    Google Scholar 

  27. Moulder, J. F., Stickle, W. F., Sobol, P. E. & Bomben, K. D. Handbook of X-ray Photoelectron Spectroscopy: A Reference Book of Standard Spectra for Identification and Interpretation of XPS Data (Physical Electronics, 1995).

    Google Scholar 

  28. Hammond, J. S., Gaarenstroom, S. W. & Winograd, N. X-ray photoelectron spectroscopic studies of cadmium- and silver-oxygen surfaces. Anal. Chem. 47, 2193–2199 (1975).

    Google Scholar 

  29. Schreder, B. et al. Raman spectroscopy of II–VI semiconductor nanostructures: CdS quantum dots. J. Raman Spectrosc. 34, 100–103 (2003).

    Google Scholar 

  30. Kumar, S., Ojha, A. K. & Singh, R. K. Synthesis and Raman signature for the formation of CdO/MnO2 (core/shell) nanostructures. J. Raman Spectrosc. 45, 717–722 (2014).

    Google Scholar 

  31. Cuscó, R. et al. Raman scattering of cadmium oxide epilayers grown by metal-organic vapor phase epitaxy. J. Appl. Phys. 107, 063519 (2010).

    Google Scholar 

  32. Williams, R. & Labib, M. E. Zinc sulfide surface chemistry: an electrokinetic study. J. Colloid Interface Sci. 106, 251–254 (1985).

    Google Scholar 

  33. Kuehnel, M. F., Wakerley, D. W., Orchard, K. L. & Reisner, E. Photocatalytic formic acid conversion on CdS nanocrystals with controllable selectivity for H2 or CO. Angew. Chem. Int. Ed. 54, 9627–9631 (2015).

    Google Scholar 

  34. Dworak, L. et al. Ultrafast charge separation at the CdSe/CdS Core/Shell quantum dot/methylviologen interface: implications for nanocrystal solar cells. J. Phys. Chem. C 115, 3949–3955 (2011).

    Google Scholar 

  35. Simon, T. et al. Redox shuttle mechanism enhances photocatalytic H2 generation on Ni-decorated CdS nanorods. Nat. Mater. 13, 1013–1018 (2014).

    Google Scholar 

  36. Speltini, A. et al. Swine sewage as sacrificial biomass for photocatalytic hydrogen gas production: explorative study. Int. J. Hydrogen Energy 39, 11433–11440 (2014).

    Google Scholar 

  37. Cai, J. & Zhang, L. Rapid dissolution of cellulose in LiOH/Urea and NaOH/Urea aqueous solutions. Macromol. Biosci. 5, 539–548 (2005).

    Google Scholar 

  38. Ramos, M. L., Caldeira, M. M. & Gil, V. M. S. NMR spectroscopy study of the complexation of D-gluconic acid with tungsten(VI) and molybdenum(VI). Carbohydr. Res. 304, 97–109 (1997).

    Google Scholar 

  39. Wölfel, R., Taccardi, N., Bösmann, A. & Wasserscheid, P. Selective catalytic conversion of biobased carbohydrates to formic acid using molecular oxygen. Green Chem. 13, 2759–2763 (2011).

    Google Scholar 

  40. Fischer, S., Leipner, H., Thümmler, K., Brendler, E. & Peters, J. Inorganic molten salts as solvents for cellulose. Cellulose 10, 227–236 (2003).

    Google Scholar 

  41. Zhao, J., Holmes, M. A. & Osterloh, F. E. Quantum confinement controls photocatalysis: a free energy analysis for photocatalytic proton reduction at CdSe nanocrystals. ACS Nano 7, 4316–4325 (2013).

    Google Scholar 

  42. Yang, J., Liu, H., Martens, W. N. & Frost, R. L. Synthesis and characterization of cobalt hydroxide, cobalt oxyhydroxide, and cobalt oxide nanodiscs. J. Phys. Chem. C 114, 111–119 (2010).

    Google Scholar 

  43. Wu, K. et al. Hole removal rate limits photodriven H2 generation efficiency in CdS-Pt and CdSe/CdS-Pt semiconductor nanorod–metal tip heterostructures. J. Am. Chem. Soc. 136, 7708–7716 (2014).

    Google Scholar 

  44. Kadam, S. R. et al. A green process for efficient lignin (biomass) degradation and hydrogen production via water splitting using nanostructured C, N, S-doped ZnO under solar light. Roy. Soc. Chem. Adv. 4, 60626–60635 (2014).

    Google Scholar 

  45. Li, C., Zhao, X., Wang, A., Huber, G. W. & Zhang, T. Catalytic transformation of lignin for the production of chemicals and fuels. Chem. Rev. 115, 11559–11624 (2015).

    Google Scholar 

  46. Müller, U., Rätzsch, M., Schwanninger, M., Steiner, M. & Zöbl, H. Yellowing and IR-changes of spruce wood as result of UV-irradiation. J. Photochem. Photobiol. B 69, 97–105 (2003).

    Google Scholar 

  47. Kumar, P., Barrett, D. M., Delwiche, M. J. & Stroeve, P. Methods for pretreatment of lignocellulosic biomass for efficient hydrolysis and biofuel production. Ind. Eng. Chem. Res. 48, 3713–3729 (2009).

    Google Scholar 

  48. Fang, X., Mark, G. & von Sonntag, C. OH radical formation by ultrasound in aqueous solutions Part I: the chemistry underlying the terephthalate dosimeter. Ultrason. Sonochem. 3, 57–63 (1996).

    Google Scholar 

  49. Goldstein, S., Aschengrau, D., Diamant, Y. & Rabani, J. Photolysis of aqueous H2O2: quantum yield and applications for polychromatic UV actinometry in photoreactors. Environ. Sci. Technol. 41, 7486–7490 (2007).

    Google Scholar 

  50. Awatani, T., Dobson, K. D., McQuillan, A. J., Ohtani, B. & Uosaki, K. In situ infrared spectroscopic studies of adsorption of lactic acid and related compounds on the TiO2 and CdS semiconductor photocatalyst surfaces from aqueous solutions. Chem. Lett. 27, 849–850 (1998).

    Google Scholar 

  51. Huang, L. et al. Dual cocatalysts loaded type I CdS/ZnS core/shell nanocrystals as effective and stable photocatalysts for H2 evolution. J. Phys. Chem. C 117, 11584–11591 (2013).

    Google Scholar 

  52. Yu, W. W., Qu, L., Guo, W. & Peng, X. Experimental determination of the extinction coefficient of CdTe, CdSe, and CdS nanocrystals. Chem. Mater. 15, 2854–2860 (2003).

    Google Scholar 

  53. Suzuki, K. et al. Reevaluation of absolute luminescence quantum yields of standard solutions using a spectrometer with an integrating sphere and a back-thinned CCD detector. Phys. Chem. Chem. Phys. 11, 9850–9860 (2009).

    Google Scholar 

  54. Reisner, E. et al. Research data supporting “Solar-driven reforming of lignocellulose to H2 with a CdS/CdOx photocatalyst”. Apollo https://doi.org/10.17863/CAM.7480 (2017).

Download references

Acknowledgements

This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group (to E.R.), the EPSRC (DTA studentships for D.W.W. and T.E.R), the Isaac Newton Trust, the German Research Foundation (to M.F.K.), the World Premier Institute Research Center Initiative (WPI), MEXT, Japan (to K.L.O.) and a Marie Curie Research fellowship (to K.H.L., GAN 701192 - VSHER). We would like to thank Mr Adam Brown (Cambridge, UK) for performing XPS measurements, Prof. Peter Hildebrandt (TU Berlin, Germany) for providing access to his laboratory to record Raman spectra and Dr Benjamin Martindale for proofreading this manuscript.

Author information

Author notes

  1. David W. Wakerley and Moritz F. Kuehnel: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, Christian Doppler Laboratory for Sustainable SynGas Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK

    David W. Wakerley, Moritz F. Kuehnel, Katherine L. Orchard, Khoa H. Ly, Timothy E. Rosser & Erwin Reisner

Authors
  1. David W. Wakerley
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Moritz F. Kuehnel
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Katherine L. Orchard
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Khoa H. Ly
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Timothy E. Rosser
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Erwin Reisner
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

D.W.W., M.F.K. and E.R. conceived the research. D.W.W. and M.F.K. performed photocatalysis and NMR experiments. D.W.W. and K.L.O. synthesized and characterized the QDs. K.L.O. executed TEM, XRD and the zeta potential analysis. K.H.L. carried out the Raman experiments. D.W.W. and T.E.R. carried out the fluorescence measurements. All authors analysed the data. D.W.W. wrote the manuscript. M.F.K., K.H.L. and E.R. added to the discussion and contributed to the preparation of the manuscript. E.R. supervised the work.

Corresponding author

Correspondence to Erwin Reisner.

Ethics declarations

Competing interests

Patent applications covering this work have been filed by Cambridge Enterprise (UK patent application numbers GB1619953.1 and GB1701130.5) that name D.W.W., M.F.K., K.L.O. and E.R. as inventors.

Supplementary information

Supplementary Information

Supplementary Tables 1–10, Supplementary Figures 1–14. (PDF 1688 kb)

Supplementary Video 1

Video of the reported system evolving H2 in the presence of a cutting from a wooden branch or paper. 3.6 nmol of ligand-free CdS QDs in DMF are injected onto each substrate and dried. The substrate was then added to 2 ml of 10 M KOH, forming CdS/CdOx. Samples were purged with N2 and irradiated using simulated solar light (AM 1.5G, 100 mW cm−2) for 1 h before filming. Filming was undertaken while irradiating with light from a nearby Kodak carousel 2020 projector. (MP4 116522 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wakerley, D., Kuehnel, M., Orchard, K. et al. Solar-driven reforming of lignocellulose to H2 with a CdS/CdOx photocatalyst. Nat Energy 2, 17021 (2017). https://doi.org/10.1038/nenergy.2017.21

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1038/nenergy.2017.21

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