Streamlined hydrogen production from biomass

Abstract

Hydrogen is playing an increasingly larger role in clean energy technologies and the emerging hydrogen economy. However, efficient and selective H2 production from renewable resources is rare so far. Herein, we describe a dehydrogenation route that is applicable to various kinds of non-food-related biomass and daily waste, such as wheat straw, corn straw, rice straw, reed, bagasse, bamboo sawdust, cardboard and newspaper. H2 yields up to 95% were achieved by a one-pot, two-step reaction with a 69 ppm molecularly defined iridium catalyst bearing an imidazoline moiety from formic acid, which was in turn obtained via a 1 v% dimethyl sulfoxide-promoted hydrolysis–oxidation of biomass. Formation of the unwanted side products CO and CH4 was no more than 22 and 2 ppm, respectively, while CO2 was captured as carbonate. The resulting hydrogen gas can be directly applied in proton exchange membrane fuel cells.

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Fig. 1: Streamlining the conversion of non-food-related biomass to electricity via H2.
Fig. 2: Volume–time profile of H2 production and its direct conversion to electricity.
Fig. 3: Kinetic experiments.
Fig. 4: Proposed mechanism of H2 production from biomass-derived FA.

Change history

  • 09 August 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

  • 05 August 2019

    An amendment to this paper has been published and can be accessed via a link at the top of the paper.

  • 30 July 2018

    In the version of this Article originally published, there were several errors in Table 1: in structure 1, the NH group bonded to the Ir should have been a H atom; the NR2 group bonded to the Ir should have been NH; in structures 2, 4 and 5, the OH groups bonded to the Ir atoms should have been OH2 groups; in structure 6 the OH2 group bonded to Ir was erroneously bonded with the below N; and in structure 10, the N=N bond should have been N–N. In structure 12 of Fig. 4, the CH2 between the two oxygen atoms should have been a CH group. Finally, the affiliations within the Supplementary Information were not consistent with those of the main text, a new Supplementary Information file has been uploaded.

References

  1. 1.

    Nikolaidis, P. & Poullikkas, A. A comparative overview of hydrogen production processes. Renew. Sust. Energ. Rev. 67, 597–611 (2017).

    CAS  Article  Google Scholar 

  2. 2.

    Stolten, D. (ed.) Hydrogen and Fuel Cells (Wiley-VCH, Weinheim, 2010).

  3. 3.

    Turner, J. A. Sustainable hydrogen production. Science 305, 972–974 (2004).

    CAS  Article  Google Scholar 

  4. 4.

    Muradov, N. Z. & Veziroğlu, T. N. “Green” path from fossil-based to hydrogen economy: an overview of carbon-neutral technologies. Int. J. Hydrogen Energy 33, 6804–6839 (2008).

    CAS  Article  Google Scholar 

  5. 5.

    Sanderson, K. Lignocellulose: a chewy problem. Nature 474, S12–S14 (2011).

    CAS  Article  Google Scholar 

  6. 6.

    Cortright, R. D., Davda, R. & Dumesic, J. A. Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water. Nature 418, 964–967 (2002).

    CAS  Article  Google Scholar 

  7. 7.

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

    CAS  Article  Google Scholar 

  8. 8.

    Sikarwar, V. S. et al. An overview of advances in biomass gasification. Energy Environ. Sci. 9, 2939–2977 (2016).

    CAS  Article  Google Scholar 

  9. 9.

    Kan, T., Strezov, V. & Evans, T. J. Lignocellulosic biomass pyrolysis: a review of product properties and effects of pyrolysis parameters. Renew. Sust. Energ. Rev. 57, 1126–1140 (2016).

    CAS  Article  Google Scholar 

  10. 10.

    Reddy, S. N., Nanda, S., Dalai, A. K. & Kozinski, J. A. Supercritical water gasification of biomass for hydrogen production. Int. J. Hydrogen Energy 39, 6912–6926 (2014).

    CAS  Article  Google Scholar 

  11. 11.

    Stonor, M. R., Ferguson, T. E., Chen, J. G. & Park, A.-H. A. Biomass conversion to H2 with substantially suppressed CO2 formation in the presence of group I & group II hydroxides and a Ni/ZrO2 catalyst. Energy Environ. Sci. 8, 1702–1706 (2015).

    CAS  Article  Google Scholar 

  12. 12.

    Woodward, J. et al. In vitro hydrogen production by glucose dehydrogenase and hydrogenase. Nat. Biotechnol. 14, 872–874 (1996).

    CAS  Article  Google Scholar 

  13. 13.

    Jonathan, W., Orr, M., Cordray, K. & Greenbaum, E. Biotechnology: enzymatic production of biohydrogen. Nature 405, 1014–1015 (2000).

    Article  Google Scholar 

  14. 14.

    Rollin, J. A. et al. High-yield hydrogen production from biomass by in vitro metabolic engineering: mixed sugars coutilization and kinetic modeling. Proc. Natl Acad. Sci. USA 112, 4964–4969 (2015).

    CAS  Article  Google Scholar 

  15. 15.

    Xia, A. et al. Fermentative hydrogen production using algal biomass as feedstock. Renew. Sust. Energ. Rev. 51, 209–230 (2015).

    CAS  Article  Google Scholar 

  16. 16.

    Liu, W. et al. High efficiency hydrogen evolution from native biomass electrolysis. Energy Environ. Sci. 9, 467–472 (2016).

    CAS  Article  Google Scholar 

  17. 17.

    Kadier, A. et al. Recent advances and emerging challenges in microbial electrolysis cells (MECs) for microbial production of hydrogen and value-added chemicals. Renew. Sust. Energ. Rev. 61, 501–525 (2016).

    CAS  Article  Google Scholar 

  18. 18.

    Sabatier, P. & Mailhe, A. Catayltic decompostion of formic acid. Compt. Rend. 152, 1212–1215 (1912).

    CAS  Google Scholar 

  19. 19.

    Grasemann, M. & Laurenczy, G. Formic acid as a hydrogen source–recent developments and future trends. Energy Environ. Sci. 5, 8171–8181 (2012).

    CAS  Article  Google Scholar 

  20. 20.

    Zhu, Q.-L. & Xu, Q. Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage. Energy Environ. Sci. 8, 478–512 (2015).

    CAS  Article  Google Scholar 

  21. 21.

    Mellmann, D., Sponholz, P., Junge, H. & Beller, M. Formic acid as a hydrogen storage material—development of homogeneous catalysts for selective hydrogen release. Chem. Soc. Rev. 45, 3954–3988 (2016).

    CAS  Article  Google Scholar 

  22. 22.

    Taccardi, N. et al. Catalytic production of hydrogen from glucose and other carbohydrates under exceptionally mild reaction conditions. Green. Chem. 12, 1150–1156 (2010).

    CAS  Article  Google Scholar 

  23. 23.

    Li, Y., Sponholz, P., Nielsen, M., Junge, H. & Beller, M. Iridium-catalyzed hydrogen production from monosaccharides, disaccharide, cellulose, and lignocellulose. ChemSusChem 8, 804–808 (2015).

    CAS  Article  Google Scholar 

  24. 24.

    McGinnis, G. D., Prince, S. E., Biermann, C. J. & Lowrimore, J. T. Wet oxidation of model carbohydrate compounds. Carbohydr. Res. 128, 51–60 (1984).

    CAS  Article  Google Scholar 

  25. 25.

    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).

    Article  Google Scholar 

  26. 26.

    Jin, F. & Enomoto, H. Rapid and highly selective conversion of biomass into value-added products in hydrothermal conditions: chemistry of acid/base-catalysed and oxidation reactions. Energy Environ. Sci. 4, 382–397 (2011).

    CAS  Article  Google Scholar 

  27. 27.

    Li, J., Ding, D.-J., Deng, L., Guo, Q.-X. & Fu, Y. Catalytic air oxidation of biomass-derived carbohydrates to formic acid. ChemSusChem 5, 1313–1318 (2012).

    CAS  Article  Google Scholar 

  28. 28.

    Albert, J., Wölfel, R., Bösmann, A. & Wasserscheid, P. Selective oxidation of complex, water-insoluble biomass to formic acid using additives as reaction accelerators. Energy Environ. Sci. 5, 7956–7962 (2012).

    CAS  Article  Google Scholar 

  29. 29.

    Tang, Z. et al. Transformation of cellulose and its derived carbohydrates into formic and lactic acids catalyzed by vanadyl cations. ChemSusChem 7, 1557–1567 (2014).

    CAS  Article  Google Scholar 

  30. 30.

    Albert, J., Lüders, D., Bösmann, A., Guldi, D. M. & Wasserscheid, P. Spectroscopic and electrochemical characterization of heteropoly acids for their optimized application in selective biomass oxidation to formic acid. Green. Chem. 16, 226–237 (2014).

    CAS  Article  Google Scholar 

  31. 31.

    Wang, W. et al. Catalytic conversion of biomass-derived carbohydrates to formic acid using molecular oxygen. Green. Chem. 16, 2614–2618 (2014).

    CAS  Article  Google Scholar 

  32. 32.

    Niu, M., Hou, Y., Ren, S., Wu, W. & Marsh, K. N. Conversion of wheat straw into formic acid in NaVO3–H2SO4 aqueous solution with molecular oxygen. Green. Chem. 17, 453–459 (2015).

    CAS  Article  Google Scholar 

  33. 33.

    Reichert, J., Brunner, B., Jess, A., Wasserscheid, P. & Albert, J. Biomass oxidation to formic acid in aqueous media using polyoxometalate catalysts-boosting FA selectivity by in-situ extraction. Energy Environ. Sci. 8, 2985–2990 (2015).

    CAS  Article  Google Scholar 

  34. 34.

    Boddien, A. et al. Efficient dehydrogenation of formic acid using an iron catalyst. Science 333, 1733–1736 (2011).

    CAS  Article  Google Scholar 

  35. 35.

    Nielsen, M. et al. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide. Nature 495, 85–89 (2013).

    CAS  Article  Google Scholar 

  36. 36.

    Wang, W.-H. et al. Formic acid dehydrogenation with bioinspired iridium complexes: a kinetic isotope effect study and mechanistic insight. ChemSusChem 7, 1976–1983 (2014).

    CAS  Article  Google Scholar 

  37. 37.

    Wang, W.-H. et al. Highly robust hydrogen generation by bioinspired Ir complexes for dehydrogenation of formic acid in water: experimental and theoretical mechanistic investigations at different pH. ACS Catal. 5, 5496–5504 (2015).

    CAS  Article  Google Scholar 

  38. 38.

    Wang, Z., Lu, S.-M., Li, J., Wang, J. & Li, C. Unprecedentedly high formic acid dehydrogenation activity on an iridium complex with an N,N′-diimine ligand in water. Chem. Eur. J. 21, 12592–12595 (2015).

    CAS  Article  Google Scholar 

  39. 39.

    Hull, J. F. et al. Reversible hydrogen storage using CO2 and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures. Nat. Chem. 4, 383–388 (2012).

    CAS  Article  Google Scholar 

  40. 40.

    Maenaka, Y., Suenobu, T. & Fukuzumi, S. Catalytic interconversion between hydrogen and formic acid at ambient temperature and pressure. Energy Environ. Sci. 5, 7360–7367 (2012).

    CAS  Article  Google Scholar 

  41. 41.

    Boddien, A., Loges, B., Junge, H. & Beller, M. Hydrogen generation at ambient conditions: application in fuel cells. ChemSusChem 1, 751–758 (2008).

    CAS  Article  Google Scholar 

  42. 42.

    Harris, D. C. (ed.) Quantitative Chemical Analysis Ch. 7, 142–161 (W. H. Freeman and Company, New York, 2010).

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Acknowledgements

This work was supported by National Nature Science Foundation of China (nos. 21472145 and 21305117) and a Leibniz fellowship. We thank W.-F. Tian, K.-H. He, Xi’an Jiaotong University for their help during the experiments. We thank L. Wang, Institute of Pulp and Paper Technology, Hubei University of Technology, China for affording various raw biomass and daily waste. We thank H.-J. Jiao, Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Z.-J. Shi, Fudan University for helpful discussion. We thank Wattecs Lab Equipment Co., Ltd. for strong support on autoclaves and constant pressure gas collectors.

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Authors

Contributions

Y.L. and M.B. conceived this project. P.Z., Y.-J.G., Y.-R.Z. and J.C. performed the experiments and analysed the data. J.C. synthesized the precursors of catalysts 5 and 6. P.Z., Y.-J.G., H.J., M.B. and Y.L. wrote the manuscript.

Corresponding authors

Correspondence to Matthias Beller or Yang Li.

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Supplementary information

Supplementary Information

Supplementary Methods; Supplementary Tables 1–8; Supplementary Figures 1–36; Supplementary references

Crystallographic data

Crystallographic data for compound [Cp*CF3IrCl2]2, CCDC reference 1522237

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Zhang, P., Guo, Y., Chen, J. et al. Streamlined hydrogen production from biomass. Nat Catal 1, 332–338 (2018). https://doi.org/10.1038/s41929-018-0062-0

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