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

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.

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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.

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.

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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).

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Affiliations

Authors

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.

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The authors declare no competing interests.

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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

41893_2020_509_MOESM2_ESM.avi

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

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.

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

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