Skip to main content

Thank you for visiting 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.

A regenerable oxide-based H2S adsorbent with nanofibrous morphology


Hydrogen sulphide is found in raw fuels such as natural gas and coal/biomass-derived syngas. It is poisonous to catalysts and corrosive to metals and therefore needs to be removed. This is often achieved using metal oxides as reactive adsorbents, but metal oxides perform poorly when subjected to repeated cycles of sulphidation and re-oxidation1,2,3,4,5,6,7,8,9,10,11,12 as a result of complex structural and chemical changes. Here, we show that Zn–Ti–O-based adsorbents with nanofibrous morphology can sustain their initial reactivity and sulphur removal capacity over multiple regeneration cycles. These nanostructured sorbents offer rapid reaction rates that overcome the gas-transport limitations of conventional pellet-based sorbents1,13 and allow all of the material to be used efficiently. Regeneration can be carried out at the same temperature as the sulphidation step because of the higher reactivity, which prevents sorbent deterioration and reduces energy use. The efficient regeneration of the adsorbent is also aided by structural features such as the growth of hierarchical nanostructures and preferential stabilization of a wurtzite phase in the sulphidation product.

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

Relevant articles

Open Access articles citing this article.

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

Figure 1: Characterization of fresh unreacted sorbent.
Figure 2: Analysis of reaction kinetics (ZT2).
Figure 3: Analysis of SEM images of reacted sorbent specimens.
Figure 4: Post-sulphidation characterization.


  1. Gibson, J. B. & Harrison, D. P. The reaction between hydrogen sulphide and spherical pellets of zinc oxide. Ind. Eng. Chem. Proc. Des. Dev. 19, 231–237 (1980).

    CAS  Article  Google Scholar 

  2. Lew, S., Jothimurugesan, K. & Flytzani-Stephanopoulos, M. High-temperature hydrogen sulphide removal from fuel gases by regenerable zinc oxide-titanium dioxide sorbents. Ind. Eng. Chem. Res. 28, 535–541 (1989).

    CAS  Article  Google Scholar 

  3. Lew, S., Sarofim, A. F. & Flytzani-Stephanopoulos, M. Sulphidation of zinc titanate and zinc oxide solids. Ind. Eng. Chem. Res. 31, 1890–1899 (1992).

    CAS  Article  Google Scholar 

  4. Siriwardane, R. V. & Poston, J. A. Interaction of H2S with zinc titanate in the presence of H2 and CO. Appl. Surf. Sci. 45, 131–139 (1990).

    CAS  Article  Google Scholar 

  5. Siriwardane, R. V., Poston, J. A. & Evans, G. Spectroscopic characterization of molybdenum-containing zinc titanate desulphurization sorbents. Ind. Eng. Chem. Res. 33, 2810–2818 (1994).

    CAS  Article  Google Scholar 

  6. Poston, J. A. A reduction in the spalling of zinc titanate desulphurization sorbents through the addition of lanthanum oxide. Ind. Eng. Chem. Res. 35, 875–882 (1996).

    CAS  Article  Google Scholar 

  7. Kobayashi, M., Shirai, H. & Nunokawa, M. Investigation on desulphurization performance and pore structure of sorbents containing zinc ferrite. Energy Fuels 11, 887–896 (1997).

    CAS  Article  Google Scholar 

  8. Atimtay, A. T. & Harrison, D. P. Desulfurization of Hot Coal Gas. Vol. 42, NATO ASI Series G (Springer, 1998).

    Book  Google Scholar 

  9. Jothimurugesan, K. & Gangwal, S. K. Regeneration of zinc titanate H2S sorbents. Ind. Eng. Chem. Res. 37, 1929–1933 (1998).

    CAS  Article  Google Scholar 

  10. Sa, L. N., Focht, G. D., Ranade, P. V. & Harrison, D. P. High-temperature desulphurization using zinc ferrite: solid structural property changes. Chem. Eng. Sci. 44, 215–224 (1989).

    CAS  Article  Google Scholar 

  11. Skrzypski, J., Bezverkhyy, J., Heintz, O. & Bellat, J. Low temperature H2S removal with metal-doped nanostructure ZnO sorbents: study of the origin of enhanced reactivity in Cu-containing materials. Ind. Eng. Chem. Res. 50, 5714–5722 (2011).

    CAS  Article  Google Scholar 

  12. Flytzani-Stephanopoulos, M., Sakbodin, M. & Wang, Z. Regenerative adsorption and removal of H2S from hot fuel gas streams by rare earth oxides. Science 312, 1508–1510 (2006).

    CAS  Article  Google Scholar 

  13. Efthimiadis, E. A. & Sotirchos, S. V. Reactivity evolution during sulphidation of porous zinc oxide. Chem. Eng. Sci. 48, 829–843 (1993).

    CAS  Article  Google Scholar 

  14. Carnes, C. L. & Klabunde, K. J. Unique chemical reactivities of nanocrystalline metal oxides toward hydrogen sulphide. Chem. Mater. 14, 1806–1811 (2002).

    CAS  Article  Google Scholar 

  15. Li, D. & Xia, Y. Fabrication of titania nanofibres by electrospinning. Nano Lett. 3, 555–560 (2003).

    CAS  Article  Google Scholar 

  16. Ramaseshan, R., Sundarrajan, S., Jose, R. & Ramakrishna, S. Nanostructured ceramics by electrospinning. J. Appl. Phys. 102, 111101 (2007).

    Article  Google Scholar 

  17. Dai, Y., Liu, W., Forno, E., Sun, Y. & Xia, Y. Ceramic nanofibres fabricated by electrospinning and their applications in catalysis, environmental science, and energy technology. Polym. Adv. Technol. 22, 326–338 (2011).

    CAS  Article  Google Scholar 

  18. Liu, R., Ye, H., Xiong, X. & Liu, H. Fabrication of TiO2/ZnO composite nanofibres by electrospinning and their photocatalytic property. Mater. Chem. Phys. 121, 432–439 (2010).

    CAS  Article  Google Scholar 

  19. Levenspiel, O. Chemical Reaction Engineering. 3rd edn (Wiley, 1999).

    Google Scholar 

  20. Zevenhoven, C. A. P., Yrjas, K. P. & Hupa, M. M. Hydrogen sulphide capture by limestone and dolomite at elevated pressure—2. Sorbent particle conversion modeling. Ind. Eng. Chem. Res. 35, 943–949 (1996).

    CAS  Article  Google Scholar 

  21. Shen, G., Chen, D. & Lee, C. J. Hierarchical saw-like ZnO nanobelt/ZnS nanowire heterostructures induced by polar surfaces. J. Phys. Chem. B 110, 15689–15693 (2006).

    CAS  Article  Google Scholar 

  22. Yin, Y. D. et al. Formation of hollow nanocrystals through the nanoscale Kirkendall effect. Science 304, 711–714 (2004).

    CAS  Article  Google Scholar 

  23. Moore, D. & Wang, Z. L. Growth of anisotropic one-dimensional ZnS nanostructures. J. Mater. Chem. 16, 3898–3905 (2006).

    CAS  Article  Google Scholar 

  24. Qadri, S. B. et al. Size-induced transition-temperature reduction in nanoparticles of ZnS. Phys. Rev. B 60, 9191–9193 (1999).

    CAS  Article  Google Scholar 

  25. Wang, Z. et al. Morphology-tuned wurtzite-type ZnS nanobelts. Nature Mater. 4, 922–927 (2005).

    CAS  Article  Google Scholar 

  26. Schultze, D., Steinike, U., Kussin, J. & Kretzschmar, U. Thermal oxidation of ZnS modifications sphalerite and wurtzite. Cryst. Res. Technol. 30, 553–558 (1995).

    CAS  Article  Google Scholar 

Download references


M.B. acknowledges the Dow Chemical Company for a graduate fellowship and thanks Q. Yang for assistance with sample preparation. P.K.J. acknowledges startup support from the Frederick Seitz Materials Research Laboratory where characterization was performed. M.A.S. acknowledges support from the NSF Science and Technology Center WaterCAMPWS.

Author information

Authors and Affiliations



M.B., J.Y. and M.A.S. developed the concept. M.B., M.A.S. and P.K.J designed the experiments. M.B. and Q.L. carried out the experiments. M.B. and J.Y. performed material characterization. Data analysis was performed by M.B., J.Y. and P.K.J. The manuscript was written by M.B., J.Y., P.K.J. and M.A.S.

Corresponding author

Correspondence to Prashant K. Jain.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 2715 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Behl, M., Yeom, J., Lineberry, Q. et al. A regenerable oxide-based H2S adsorbent with nanofibrous morphology. Nature Nanotech 7, 810–815 (2012).

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI:

This article is cited by


Quick links

Find nanotechnology articles, nanomaterial data and patents all in one place. Visit Nano by Nature Research