Open Access[Ln 6 O 8 ] Cluster‐Encapsulating Polyplumbites as New Polyoxometalate Members and Record Inorganic Anion‐Exchange Materials for ReO 4 − Sequestration
Author(s) -
Lin Jian,
Zhu Lin,
Yue Zenghui,
Yang Chuang,
Liu Wei,
AlbrechtSchmitt Thomas E.,
Wang JianQiang,
Wang Shuao
Publication year - 2019
Publication title -
advanced science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.388
H-Index - 100
ISSN - 2198-3844
DOI - 10.1002/advs.201900381
Subject(s) - polyoxometalate , sorption , perrhenate , cluster (spacecraft) , nuclear fission product , crystallography , chemistry , actinide , crystal structure , ion , single crystal , metal , ion exchange , inorganic chemistry , rhenium , radiochemistry , catalysis , fission products , adsorption , organic chemistry , computer science , programming language
Various types of polyoxometalates (POMs) have been synthesized since the 19th century, but their assortment has been mostly limited to Groups 5 and 6 metals. Herein, a new family of POMs composed of a carbon group element as the addenda atoms with two distinct phases, LnPbOClO 4 ‐1 (Ln = Sm to Ho, Y) and LnPbOClO 4 ‐2 (Ln = Er and Tm) is reported. Both structures are built from [Ln 6 O 8 ] rare‐earth metal hexamers being incorporated in [Pb 18 O 32 ]/[Pb 12 O 24 ] polyplumbites, and unbound perchlorates as charge‐balancing anions. Impressively, YPbOClO 4 ‐1 and ErPbOClO 4 ‐2 exhibit exceptional uptake capacities (434.7 and 427.7 mg g −1 ) toward ReO 4 − , a chemical surrogate for the key radioactive fission product in the nuclear fuel cycle 99 TcO 4 − , which are the highest values among all inorganic anion‐exchange materials reported until now. The sorption mechanism is clearly elucidated and visualized by single‐crystal‐to‐single‐crystal structural transformation from ErPbOClO 4 ‐2 to a perrhenate‐containing complex ErPbOReO 4 , revealing a unique ReO 4 − uptake selectivity driven by specific interaction within Pb···O‐ReO 3 − bonds.