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:

Multi-heteroatom-doped carbon from waste-yeast biomass for sustained water splitting

Nature Sustainability volume 3, pages 556–563 (2020)Cite this article

Subjects

Abstract

Producing hydrogen in clean, affordable and safe manners without damaging the environment can help address the challenge of meeting a growing energy demand sustainably. Yeast biomass-derived materials—such as multi-heteroatoms (nitrogen, sulfur and phosphorus) doped carbon (MHC) catalysts from waste biomass—can help develop efficient, eco-friendly and economical catalysts to improve the sustainability of hydrogen production. Here we report hydrogen and oxygen production in 1 M potassium hydroxide using ruthenium single atoms (RuSAs) along with Ru nanoparticles (RuNPs) embedded in MHC (RuSAs + RuNPs@MHC) as a cathode and magnetite (Fe3O4) supported on MHC (Fe3O4@MHC) as an anode. The RuSAs + RuNPs@MHC catalyst outperforms the state-of-the-art commercial platinum on carbon catalyst for hydrogen evolution reaction in terms of overpotential, exchange current density, Tafel slope and durability. Furthermore, compared with industrially adopted catalysts (that is, iridium oxide), the Fe3O4@MHC catalyst displays outstanding oxygen evolution reaction activity. For whole water splitting, it requires a solar voltage of 1.74 V to drive ~ 30 mA, along with remarkable long-term stability in the presence (12 h) and absence (58 h) of outdoor-sunlight exposure, as a promising strategy towards a sustainable energy development.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Waste-yeast cells.
Fig. 2: Structural and chemical characterizations of R-2.
Fig. 3: HER polarization curves of catalysts loaded on GSEs (95% iR compensation).
Fig. 4: Structural and chemical characterizations of F-2.
Fig. 5: OER electrocatalytic performance (95% iR compensation).
Fig. 6: Overall water-splitting performance in the presence and absence of a solar panel.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available within the article, its Supplementary Information file and from the corresponding author upon reasonable request. Source Data are provided with this paper.

References

  1. Blakemore, J. D., Crabtree, R. H. & Brudvig, G. W. Molecular catalysts for water oxidation. Chem. Rev. 115, 12974–13005 (2015).

    Article  CAS  Google Scholar 

  2. Peng, W. et al. Managing China’s coal power plants to address multiple environmental objectives. Nat. Sustain. 1, 693–701 (2018).

    Article  Google Scholar 

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

    Article  Google Scholar 

  4. World Energy Outlook 2015 (International Energy Agency, 2015).

  5. Song, F. et al. Transition metal oxides as electrocatalysts for the oxygen evolution reaction in alkaline solutions: an application-inspired renaissance. J. Am. Chem. Soc. 140, 7748–7759 (2018).

    Article  CAS  Google Scholar 

  6. Tiwari, J. N. et al. Multicomponent electrocatalyst with ultralow Pt loading and high hydrogen evolution activity. Nat. Energy 3, 773–782 (2018).

    Article  CAS  Google Scholar 

  7. Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nat. Chem. 1, 37–46 (2009).

    Article  Google Scholar 

  8. Hunter, B. M., Gray, H. B. & Müller, A. M. Earth-abundant heterogeneous water oxidation catalysts. Chem. Rev. 116, 14120–14136 (2016).

    Article  CAS  Google Scholar 

  9. Sultan, S. et al. Superb water splitting activity of the electrocatalyst Fe3Co(PO4)4 designed with computation aid. Nat. Commun. 10, 5195 (2019).

    Article  Google Scholar 

  10. Georgakilas, V., Perman, J. A., Tucek, J. & Zboril, R. Broad family of carbon nanoallotropes: classification, chemistry, and applications of fullerenes, carbon dots, nanotubes, graphene, nanodiamonds, and combined superstructures. Chem. Rev. 115, 4744–4822 (2015).

    Article  CAS  Google Scholar 

  11. Goldfarb, J. L., Dou, G., Salari, M. & Grinstaff, M. W. Biomass-based fuels and activated carbon electrode materials: an integrated approach to green energy systems. ACS Sustain. Chem. Eng. 5, 3046–3054 (2017).

    Article  CAS  Google Scholar 

  12. Wu, X.-L. et al. Biomass-derived sponge-like carbonaceous hydrogels and aerogels for supercapacitors. ACS Nano 7, 3589–3597 (2013).

    Article  CAS  Google Scholar 

  13. Schneegurt, M. A. et al. Biomass byproducts for the remediation of wastewaters contaminated with toxic metals. Environ. Sci. Technol. 35, 3786–3791 (2001).

    Article  CAS  Google Scholar 

  14. Aguilar-Uscanga, B. & François, J. M. A study of the yeast cell wall composition and structure in response to growth conditions and mode of cultivation. Lett. Appl. Microbiol. 37, 268–274 (2003).

    Article  CAS  Google Scholar 

  15. Morgan, D. J. Resolving ruthenium: XPS studies of common ruthenium materials. Surf. Interface Anal. 47, 1072–1079 (2015).

    Article  CAS  Google Scholar 

  16. Li, R., Wei, Z. & Gou, X. Nitrogen and phosphorus dual-doped graphene/carbon nanosheets as bifunctional electrocatalysts for oxygen reduction and evolution. ACS Catal. 5, 4133–4142 (2015).

    Article  CAS  Google Scholar 

  17. Qie, L. et al. Sulfur-doped carbon with enlarged interlayer distance as a high-performance anode material for sodium-ion batteries. Adv. Sci. 2, 1500195 (2015).

    Article  Google Scholar 

  18. Peng, H. et al. High performance Fe- and N- doped carbon catalyst with graphene structure for oxygen reduction. Sci. Rep. 3, 1765 (2013).

    Article  Google Scholar 

  19. Song, P., Zhang, Y., Pan, J., Zhuang, L. & Xu, W. Cheap carbon black-based high-performance electrocatalysts for oxygen reduction reaction. Chem. Commun. 51, 1972–1975 (2015).

    Article  CAS  Google Scholar 

  20. Yang, F., Chi, C., Wang, C. X., Wang, Y. & Li, Y. F. High graphite N content in nitrogen-doped graphene as an efficient metal-free catalyst for reduction of nitroarenes in water. Green Chem. 18, 4254–4262 (2016).

    Article  CAS  Google Scholar 

  21. Sultan, S. et al. Highly efficient oxygen reduction reaction activity of graphitic tube encapsulating nitrided CoxFey alloy. Adv. Energy Mater. 8, 1801002 (2018).

    Article  Google Scholar 

  22. McCrory, C. C. L. et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am. Chem. Soc. 137, 4347–4357 (2015).

    Article  CAS  Google Scholar 

  23. Voiry, D. et al. The role of electronic coupling between substrate and 2D MoS2 nanosheets in electrocatalytic production of hydrogen. Nat. Mater. 15, 1003–1009 (2016).

    Article  CAS  Google Scholar 

  24. Zheng, Y. et al. Toward design of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution. ACS Nano 8, 5290–5296 (2014).

    Article  CAS  Google Scholar 

  25. Duan, J., Chen, S., Jaroniec, M. & Qiao, S. Heteroatom-doped graphene-based materials for energy-relevant electrocatalytic processes. ACS Catal. 5, 5207–5234 (2015).

    Article  CAS  Google Scholar 

  26. Jiao, Y., Zeng, Y., Davey, K. & Qiao, S.-Z. Activity origin and catalyst design principles for electrocatalytic hydrogen evolution on heteroatom-doped graphene. Nat. Energy 1, 16130 (2016).

    Article  CAS  Google Scholar 

  27. Qu, K. et al. Promotion of electrocatalytic hydrogen evolution reaction on nitrogen-doped carbon nanosheets with secondary heteroatoms. ACS Nano 11, 7293–7300 (2017).

    Article  CAS  Google Scholar 

  28. Sultan, S. et al. Single atoms and clusters based nanomaterials for hydrogen evolution, oxygen evolution reactions, and full water splitting. Adv. Energy Mater. 9, 1900624–1900671 (2019).

    Article  Google Scholar 

  29. Wu, R. et al. NaCl protected synthesis of 3D hierarchical metal-free porous nitrogen-doped carbon catalysts for the oxygen reduction reaction in acidic electrolyte. Chem. Commun. 55, 9023–9026 (2019).

    Article  CAS  Google Scholar 

  30. Zhang, J. et al. Heteroatom (nitrogen/sulfur)-doped graphene as an efficient electrocatalyst for oxygen reduction and evolution reactions. Catalysts 8, 475–484 (2018).

    Article  Google Scholar 

  31. Chai, G.-L. et al. Active sites engineering leads to exceptional ORR and OER bifunctionality in P,N co-doped graphene frameworks. Energy Environ. Sci. 10, 1186–1195 (2017).

    Article  CAS  Google Scholar 

  32. Cao, J. M., Feng, Y. Q., Liu, B. Y. & Li, H. G. Carbon skeleton doped with Co, N, S and P as efficient electrocatalyst for oxygen evolution reaction. Sci. China Mater. 61, 686–696 (2018).

    Article  CAS  Google Scholar 

  33. Davodi, F., Tavakkoli, M., Lahtinen, J. & Kallio, T. Straightforward synthesis of nitrogen-doped carbon nanotubes as highly active bifunctional electrocatalysts for full water splitting. J. Catal. 353, 19–27 (2017).

    Article  CAS  Google Scholar 

  34. Yang, H. B. et al. Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: development of highly efficient metal-free bifunctional electrocatalyst. Sci. Adv. 2, e1501122 (2016).

    Article  Google Scholar 

  35. Kang, Z. et al. Engineering an Earth-abundant element-based bifunctional electrocatalyst for highly efficient and durable overall water splitting. Adv. Funct. Mater. 29, 1807031 (2019).

    Article  Google Scholar 

  36. Zhang, X. et al. Highly active core–shell carbon/NiCo2O4 double microtubes for efficient oxygen evolution reaction: ultralow overpotential and superior cycling stability. Small 15, 1903297 (2019).

    Article  CAS  Google Scholar 

  37. Zhang, W., Wu, Y., Qi, J., Chen, M. & Cao, R. A thin NiFe hydroxide film formed by stepwise electrodeposition strategy with significantly improved catalytic water oxidation efficiency. Adv. Energy Mater. 7, 1602547 (2017).

    Article  Google Scholar 

  38. Campos-Roldán, C. A., González-Huerta, R. G. & Alonso-Vante, N. Experimental protocol for HOR and ORR in alkaline electrochemical measurements. J. Electrochem. Soc. 165, J3001–J3007 (2018).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by NRF (National Honor Scientist Program: 2010-0020414). We appreciate the use of the beamline 6D at the Pohang Accelerator Laboratory (PAL).

Author information

Authors and Affiliations

  1. Center for Superfunctional Materials, Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Korea

    Jitendra N. Tiwari, Ngoc Kim Dang, Siraj Sultan, Pandiarajan Thangavel & Kwang S. Kim

  2. UNIST Central Research Facilities, UNIST, Ulsan, Korea

    Hu Young Jeong

Authors
  1. Jitendra N. Tiwari
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ngoc Kim Dang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Siraj Sultan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Pandiarajan Thangavel
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Hu Young Jeong
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Kwang S. Kim
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.N.T. planned the experiment, physical characterization and electrochemical measurements and analysed the data. N.K.D. synthesized the catalysts and electrochemical measurements. S.S. discussed the results. P.T. performed full water splitting and data analysis. H.Y.J. further refined STEM measurements. J.N.T. and K.S.K. wrote the manuscript. K.S.K. supervised the project.

Corresponding authors

Correspondence to Jitendra N. Tiwari or Kwang S. Kim.

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.

Extended data

Extended Data Fig. 1 Photographs for large-scale synthesis of catalysts using yeast biomass.

a, R-2 (RuSAs+RuNPs@MHC)40mg. b, F-2 (Fe3O4@MHC)1.4g.

Extended Data Fig. 2 SEM images.

SEM images of (a) R-0 (without glutaraldehyde/NaCl) (b) R-4 (without glutaraldehyde), (c) R-5 (without hydrothermal process), and (d) R-2 (with glutaraldehyde/NaCl). Scale bars in 2 µm.

Extended Data Fig. 3 High-angle-annular-dark-field (HAADF) image.

High-angle-annular-dark-field (HAADF) image of R-2 and the corresponding energy-dispersive X-ray spectroscopy (EDS) elemental mapping images show that the sample contains C, Ru, S, N and P. Scale bars in 1 µm.

Extended Data Fig. 4 X-ray photoelectron spectroscopy (XPS) spectra.

a, XPS full survey spectrum of the R-2 sample and the corresponding core-level spectra of Ru 2p (b), C 1s (c), P 2p (d), S 2p (e), and N 1s (f).

Extended Data Fig. 5 X-ray diffraction (XRD) spectra of synthesized catalysts with different amount of Ru precursors.

a, R-1(RuSAs+RuNPs@MHC)35mg. b, R-2 (RuSAs+RuNPs@MHC)40mg. c, R-3 (RuNPs@MHC)45mg. For each spectrum, all diffraction peaks at 38.4°, 42.2°, 44.0°, 58.3°, 69.4°, 78.4°, and 84.7° correspond to the (100), (002), (101), (102), (110), (103), and (112) planes of a hexagonal-close packed (hcp) Ru crystal (JCPDS 03-065-7646). It confirms that the hcp Ru crystal structure remains unaffected after using the various amount of Ru precursors. However, the peak shape is strongly affected by Ru precursors. When we used a higher amount of Ru precursor (R-3), the peak broadening decreases and the sharpness of the peak increases, indicative of increase in crystallite size.

Extended Data Fig. 6 X-ray photoelectron spectroscopy (XPS) spectra.

a, XPS full survey spectrum of R-1 sample and the corresponding core-level spectra of Ru 2p (b), C 1s (c), P 2p (d), S 2p (e), and N 1s (f).

Extended Data Fig. 7 X-ray photoelectron spectroscopy (XPS) spectra.

a, XPS full survey spectrum of R-3 sample and the corresponding core-level spectra of Ru 2p (b), C 1s (c), P 2p (d), S 2p (e), and N 1s (f).

Extended Data Fig. 8 SEM and TEM images of R-1.

a, SEM image. b, TEM image of carbonized individual yeast cells. c, HRTEM image taken from the top edge of the carbonized individual yeast cells in (b). Inset shows the particle size distribution of RuNPs. d, AC-HAADF-STEM image showing the presence of single atoms and NPs in R-1. e, High-angle-annular-dark-field (HAADF) image and the corresponding energy-dispersive X-ray spectroscopy (EDS) elemental mapping images show that the sample contains C, Ru, N, P and S. Scale bars in (e): 1 µm. When we use 35 mg Ru precursor, the single atoms (SAs) are easily detected.

Extended Data Fig. 9 SEM and TEM images of R-3.

a, SEM image. b, TEM image of carbonized individual yeast cells. c, HRTEM image taken from the top edge of the carbonized individual yeast cells in (b). Inset shows the particle size distribution of RuNPs. d, AC-HAADF-STEM image showing the absence of single atoms R-3. e, High-angle-annular-dark-field (HAADF) image and the corresponding energy-dispersive X-ray spectroscopy (EDS) elemental mapping images show that the sample contains C, Ru, N, P and S. Scale bars in (e): 1 µm. When we use 45 mg Ru precursor, the single atoms (SAs) are fully disappeared due to aggration of nanoparticles.

Extended Data Fig. 10 TEM and HAADF images of Ru/GO.

a, TEM image. b, HRTEM image. c, High-angle-annular-dark-field (HAADF) image and the corresponding energy-dispersive X-ray spectroscopy (EDS) elemental mapping images show that the sample contains C and Ru. Scale bars in (c): 500 nm.

Supplementary information

Supplementary Information

Supplementary Figs. 1–17, Tables 1–3, Note 1 and methods.

Supplementary Video 1

Demonstration of full water splitting by solar panel in alkaline electrolyte.

Source data

Source Data Fig. 2

Unmodified experimental electron energy loss spectra (EELS) data.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Tiwari, J.N., Dang, N.K., Sultan, S. et al. Multi-heteroatom-doped carbon from waste-yeast biomass for sustained water splitting. Nat Sustain 3, 556–563 (2020). https://doi.org/10.1038/s41893-020-0509-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41893-020-0509-6

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