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Biogenic Realgar As 4 S 4 Molecular Clusters Formed by a One‐Pot Microbial‐Driven Process as a Li‐Ion Storage Material
Author(s) -
Kim TaeYang,
Ahn Hyungju,
Jeon Jeongsuk,
Kim Mi Sug,
Kim Min Gyu,
Hur HorGil
Publication year - 2017
Publication title -
advanced sustainable systems
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.499
H-Index - 24
ISSN - 2366-7486
DOI - 10.1002/adsu.201700056
Subject(s) - realgar , ion , materials science , cluster (spacecraft) , chemical engineering , nanotechnology , crystallography , chemistry , mineralogy , organic chemistry , computer science , engineering , programming language
Eco‐efficient biogenic strategies for the removal of toxic elements result in the formation of unique nano/microstructured materials with dual functionalities for energy conversion and storage. In one pot under aqueous conditions, the bacterium Shewanella sp. strain HN‐41 precipitates nanostructured arsenic sulfides (realgar, As 4 S 4 ) and its reduced graphene oxide nanocomposites. Considering the unique structural characteristics of the freestanding molecular‐cage‐like single clusters, the biogenic realgar structure is utilized as an independent anode unit since each cluster integrates four faceted five‐membered As 4 S 4 rings, providing a short diffusion length into each cluster and facile chemical binding onto the sulfur atoms with lone pairs of electrons. Here, the role of the biogenic realgar structure in the reversible uptake and release of Li ions into and from the molecular‐cage‐like single clusters is investigated. Using in situ As K‐edge X‐ray absorption fine structure analyses, the Li‐ion uptake ability of realgar As 4 S 4 (As 4 S 4 ↔Li 20 As 4 S 4 ) is achieved through a two‐step mechanism: (1) molecular clustering to form Li 8 As 4 S 4 (≈500 mA h g −1 ) and (2) alloying to form Li 12 As 4 only in the interior of the single clusters (≈750 mA h g −1 ). Thus, the bacteria‐driven biological synthesis under mild conditions can provide an alternative synthetic strategy and promotes easy scale‐up for nanostructured materials.