journal article·2017-11Open access

Carbon-decorated iron oxide hollow granules formed using a silk fibrous template: lithium-oxygen battery and wastewater treatment applications

Taek-Seung Kim, Gwang-Hee Lee, Seun Lee, Yoon-Sung Choi, Jae-Chan Kim, Hee Jo Song, Dong-Wan Kim

NPG Asia Materials· Volume 9· Issue 11

Abstract

Hierarchical nanoarchitecture and phase control of iron oxides are important approaches for achieving multi-functionality for various applications. Herein, rice-grain-shaped iron oxide hollow structures were synthesized via a hydrothermal process using a silk fibrous template, and the crystalline phases (α-Fe2O3, Fe3O4) were controlled by annealing. These structures were applied in a lithium-oxygen battery cathode and as adsorbents for wastewater treatment. The porosity, hollow interior, surface area, surface chemical composition and efficient carbon matrix of the C/Fe3O4 hollow granules obtained by annealing under Ar atmosphere were favorable for enhancing the oxygen reduction and evolution kinetics when applied as an electrocatalyst for lithium-oxygen batteries, and also led to superior adsorption of organic pollutants (Rhodamine B) from an aqueous medium. The C/Fe3O4 hollow granules were uniformly distributed and confined in the 3D nanoarchitecture; this morphology can offer rapid ion transport with improved electronic and chemical kinetics as well as superior adsorption of organic pollutants. Hollow nanoparticles of iron oxide can power up both batteries and water purification thanks to a silk-based synthetic strategy. Dong-Wan Kim from Korea University extracted fibroin proteins from silkworm cocoons to produce thin assemblies of beta sheets terminated by peptide chains. When mixed with an iron chloride precursor and heated in a sealed autoclave, the silk proteins aggregated into spherical micelles, which served as crystallization templates. Strong interactions between metal ions and micelles directed iron oxide to assemble into rice-grain-shaped structures that gradually ‘ripened’ with interior void spaces. Final annealing in an argon atmosphere produced carbon-magnetite composites with a large distribution of electrocatalytic sites useful for lithium-oxygen battery anodes. The three-dimensional hollow nanoarchitectures also proved efficient at removing carcinogenic rhodamine B dye from wastewater. Iron oxides were designed to the rice-grain-shaped hollow structures with hierarchical pores and highly aligned nano/micro-structures using silk fibrous templates to impose multi-functional materials for the electrocatalysts for Li-O2 batteries and the adsorbents of organic pollutants.
Source: openalex_inverted_index · Quality: baseline

Research context

OpenAlex topics: Advanced Photocatalysis Techniques · Supercapacitor Materials and Fabrication · Iron oxide chemistry and applications

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

References (40)

Show source-provided references
1. Shim, H.-W., Park, S., Song, H. J., Kim, J.-C., Jang, E., Hong, K. S., Kim, T. D. & Kim, D.-W. Biomineralized multifunctional magnetite/carbon microspheres for applications in Li-ion Batteries and water treatment. Chem. Eur. J. 21, 4655–4663 (2015).10.1002/chem.201406267 ↗
2. Lee, G.-H., Park, J.-G., Sung, Y.-M., Chung, K. Y., Cho, W. I. & Kim, D.-W. Enhanced cycling performance of an Fe0/Fe3O4 nanocomposite electrode for lithium-ion batteries. Nanotechnology 20, 295205 (2009).10.1088/0957-4484/20/29/295205 ↗
3. Ling, D., Lee, N. & Hyeon, T. Chemical synthesis and assembly of uniformly sized iron oxide nanoparticles for medical applications. Acc. Chem. Res. 48, 1276–1285 (2015).10.1021/acs.accounts.5b00038 ↗
4. Tilley, S. D., Cornuz, M., Sivula, K. & Gratzel, M. Light-induced water splitting with hematite: improved nanostructure and iridium oxide catalysis. Angew. Chem. 122, 6549–6552 (2010).10.1002/ange.201003110 ↗
5. Cesar, I., Kay, A., Martinez, J. A. G. & Gratzel, M. Translucent thin film Fe2O3 photoanodes for efficient water splitting by sunlight: nanostructure-directing effect of Si-doping. J. Am. Chem. Soc. 128, 4582–4583 (2006).10.1021/ja060292p ↗
6. Cornell, R. M. & Schwertmann, U. The iron oxides: structure, properties, reactions, occurrence and uses, Wiley-VCH, Weinheim: Germany, (2003).10.1002/3527602097 ↗
7. Santos-Carballal, D., Roldan, A., Grau-Crespo, R. & Leeuw, N. H. A DFT study of the structures, stabilities and redox behaviour of the major surfaces of magnetite Fe3O4 . Phys. Chem. Chem. Phys. 16, 21082–21097 (2014).10.1039/C4CP00529E ↗
8. Parkinson, G. S., Novotny, Z., Jacobson, P., Schmid, M. & Diebold, U. Room temperature water splitting at the surface of magnetite. J. Am. Chem. Soc. 133, 12650–12655 (2011).10.1021/ja203432e ↗
9. Wang, P. & Lo, Irene M.C. Synthesis of mesoporous magnetic γ-Fe2O3 and its application to Cr(VI) removal from contaminated water. Water Res. 43, 3727–3734 (2009).10.1016/j.watres.2009.05.041 ↗
10. Nassar, N. N. Kinetics, equilibrium and thermodynamic studies on the adsorptive removal of nickel, cadmium and cobalt from wastewater by superparamagnetic iron oxide nanoadsorbents. Can. J. Chem. Eng. 90, 1231–1238 (2012).10.1002/cjce.20613 ↗
11. Yadanaparthi, S. K. R., Graybill, D. & von Wandruszka, R. Adsorbents for the removal of arsenic, cadmium, and lead from contaminated waters. J. Hazard. Mater. 171, 1–15 (2009).10.1016/j.jhazmat.2009.05.103 ↗
12. Prasad, R., Pandey, R. & Barman, I. Engineering tailored nanoparticles with microbes: quo vadis? WIREs Nanomed. Nanobiotechnol. 8, 316–330 (2016).10.1002/wnan.1363 ↗
13. Fei, X., Li, W., Shao, Z., Seeger, S., Zhao, D. & Chen, X. Protein biomineralized nanoporous inorganic mesocrystals with tunable hierarchical nanostructures. J. Am. Chem. Soc. 136, 15781–15786 (2014).10.1021/ja509334x ↗
14. Wang, B., Chen, J. S., Wu, H. B., Wang, Z. & Lou, X. W. Quasiemulsion-templated formation of α-Fe2O3 hollow spheres with enhanced lithium storage properties. J. Am. Chem. Soc. 133, 17146–17148 (2011).10.1021/ja208346s ↗
15. Lou, X. W., Archer, L. A. & Yang, Z. Hollow micro-/nanostructures: synthesis and applications. Adv. Mater. 20, 3987–4019 (2008).10.1002/adma.200800854 ↗
16. Ma, F.-X., Hu, H., Wu, H. B., Xu, C.-Y., Xu, Z., Zhen, L. & Lou, X. W. (D. Formation of uniform Fe3O4 hollow spheres organized by ultrathin nanosheets and their excellent lithium storage properties. Adv. Mater. 27, 4097–4101 (2015).10.1002/adma.201501130 ↗
17. Wang, B., Wu, H., Yu, L., Xu, R., Lim, T.-T. & Lou, X. W. Template-free formation of uniform urchin-like α-FeOOH hollow spheres with superior capability for water treatment. Adv. Mater. 24, 1111–1116 (2012).10.1002/adma.201104599 ↗
18. Xu, J.-J., Xu, D., Wang, Z.-L., Wang, H.-G., Zhang, L.-L. & Zhang, X.-B. Synthesis of perovskite-based porous La0.75Sr0.25MnO3 nanotubes as a highly efficient electrocatalyst for rechargeable lithium–oxygen batteries. Angew. Chem. Int. Ed. 52, 3887–3890 (2013).10.1002/anie.201210057 ↗
19. Cao, S.-W. & Zhu, Y.-J. Hierarchically nanostructured α-Fe2O3 hollow spheres: preparation, growth mechanism, photocatalytic property, and application in water treatment. J. Phys. Chem. C 112, 6253–6257 (2008).10.1021/jp8000465 ↗
20. Koo, B., Xiong, H., Slater, M. D., Prakapenka, V. B., Balasubramanian, M., Podsiadlo, P., Johnson, C. S., Rajh, T. & Shevchenko, E. V. Hollow iron oxide nanoparticles for application in lithium ion batteries. Nano Lett. 12, 2429–2435 (2012).10.1021/nl3004286 ↗
21. Zhang, J., Luan, Y., Lyu, Z., Wang, L., Xu, L., Yuan, K., Pan, F., Lai, M., Liu, Z. & Chen, W. Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries. Nanoscale 7, 14881–14888 (2015).10.1039/C5NR02983J ↗
22. Cheng, C., Shao, Z. & Vollrath, F. Silk fibroin-regulated crystallization of calcium carbonate. Adv. Funct. Mater. 18, 2172–2179 (2008).10.1002/adfm.200701130 ↗
23. Shen, Y., Johnson, M. A. & Martin, D. C. Microstructural characterization of Bombyx mori silk fibers. Macromolecules 31, 8857–8864 (1998).10.1021/ma980281j ↗
24. Jin, H.-J. & Kaplan, D. L. Mechanism of silk processing in insects and spiders. Nature 424, 1057–1061 (2003).10.1038/nature01809 ↗
25. Nguyen, A. T., Huang, Q.-L., Yang, Z., Lin, N., Xu, G. & Liu, X. Y. Crystal networks in silk fibrous materials: from hierarchical structure to ultra performance. Small 11, 1039–1054 (2015).10.1002/smll.201402985 ↗
26. Löwen, H. Colloidal soft matter under external control. J. Phys. Condens. Matter 13, R415–R432 (2001).10.1088/0953-8984/13/24/201 ↗
27. Ochi, A., Hossain, K. S., Magoshi, J. & Nemoto, N. Rheology and dynamic light scattering of silk fibroin solution extracted from the middle division of Bombyx mori silkworm. Biomacromolecules 3, 1187–1196 (2002).10.1021/bm020056g ↗
28. Zhang, C., Zhao, S., Jin, C., Koh, A. L., Zhou, Y., Xu, W., Li, Q., Xiong, Q., Peng, H. & Liu, Z. Direct growth of large-area graphene and boron nitride heterostructures by a co-segregation method. Nat. Commun. 6, 6519 (2015).10.1038/ncomms7519 ↗
29. Park, J. E., Lee, G.-H., Choi, M., Dar, M. A., Shim, H.-W. & Kim, D.-W. Comparison of catalytic performance of different types of graphene in Li-O2 batteries. J. Alloy. Compd. 647, 231–237 (2015).10.1016/j.jallcom.2015.05.200 ↗
30. Lee, J.-H., Black, R., Popov, G., Pomerantseva, E., Nan, F., Botton, G. A. & Nazar, L. F. The role of vacancies and defects in Na0.44MnO2 nanowire catalysts for lithium–oxygen batteries. Energy Environ. Sci. 5, 9558–9565 (2012).10.1039/c2ee21543h ↗
31. Lee, G.-H., Lee, S., Kim, J.-C., Kim, D. W., Kang, Y. & Kim, D.-W. MnMoO4 electrocatalysts for superior long-life and high-rate lithium-oxygen batteries. Adv. Energy Mater. 7, 1601741 (2016).10.1002/aenm.201601741 ↗
32. Song, K., Jung, J., Heo, Y.-U., Leze, Y. C., Cho, K. & Kang, Y.-M. α-MnO2 nanowire catalysts with ultra-high capacity and extremely low overpotential in lithium–air batteries through tailored surface arrangement. Phys. Chem. Chem. Phys. 15, 20075–20079 (2013).10.1039/c3cp53754d ↗
33. Gao, R., Liu, L., Hu, Z., Zhang, P., Cao, X., Wang, B. & Liu, X. The role of oxygen vacancies in improving the performance of CoO as a bifunctional cathode catalyst for rechargeable Li-O2 batteries. J. Mater. Chem. A 3, 17598–17605 (2015).10.1039/C5TA03885E ↗
34. Banger, K. K., Yamashita, Y., Mori, K., Peterson, R. L., Leedham, T., Rickard, J. & Sirringhaus, H. Low-temperature, high-performance solution-processed metal oxide thin-film transistors formed by a ‘sol–gel on chip’ process. Nat. mater. 10, 45–50 (2011).10.1038/nmat2914 ↗
35. Bruce, P. G., Freunberger, S. A., Hardwick, L. J. & Tarascon, J.-M. Li-O2 and Li-S batteries with high energy storage. Nat. mater. 11, 19–29 (2012).10.1038/nmat3191 ↗
36. Ding, J., Li, B., Liu, Y., Yan, X., Zeng, S., Zhang, X., Hou, L., Cai, Q. & Zhang, J. Fabrication of Fe3O4@reduced graphene oxide composite via novel colloid electrostatic self-assembly process for removal of contaminants from water. J. Mater. Chem. A 3, 832–839 (2015).10.1039/C4TA04297B ↗
37. Nassar, N. N. Kinetics, mechanistic, equilibrium, and thermodynamic studies on the adsorption of acid red dye from wastewater by γ-Fe2O3 nanoadsorbents. Sep. Sci. Technol. 45, 1092–1103 (2010).10.1080/01496391003696921 ↗
38. Ho, Y. S. & McKay, G. Pseudo-second order model for sorption processes. Process Biochem. 34, 451–465 (1999).10.1016/S0032-9592(98)00112-5 ↗
39. Chen, W., Duan, L., Wang, L. & Zhu, D. Adsorption of hydroxyl- and amino-substituted aromatics to carbon nanotubes. Environ. Sci. Technol. 42, 6862–6868 (2008).10.1021/es8013612 ↗
40. Hunter, C. A. & Sanders, J. K. M. The Nature of π–π interactions. J. Am. Chem. Soc. 112, 5525–5534 (1990).10.1021/ja00170a016 ↗