Successful Decontamination of 99TcO4− in Groundwater at Legacy Nuclear Sites by a Cationic Metal‐Organic Framework with Hydrophobic Pockets. (12th March 2019)

• Record Type: Journal Article
• Authors: Sheng, Daopeng; Zhu, Lin; Dai, Xing; Xu, Chao; Li, Peng; Pearce, Carolyn I.; Xiao, Chengliang; Chen, Jing; Zhou, Ruhong; Duan, Tao; Farha, Omar K.; Chai, Zhifang; Wang, Shuao
• Is Part Of: Angewandte Chemie. Volume 131:Number 15(2019)
• Page Start: 5022
• Page End: 5026
• Publication Date: 2019-03-12
• Subjects: Anionenaustausch -- Kationische Gerüste -- Metallorganische Gerüste -- Pertechnetat -- Radioaktiver Abfall; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201814640
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 99 Tc contamination at legacy nuclear sites is a serious and unsolved environmental issue. The selective remediation of 99 TcO4 − in the presence of a large excess of NO3 − and SO4 2− from natural waste systems represents a significant scientific and technical challenge, since anions with a higher charge density are often preferentially sorbed by traditional anion‐exchange materials. We present a solution to this challenge based on a stable cationic metal‐organic framework, SCU‐102 (Ni2 (tipm)3 (NO3 )4 ), which exhibits fast sorption kinetics, a large capacity (291 mg g −1 ), a high distribution coefficient, and, most importantly, a record‐high TcO4 − uptake selectivity. This material can almost quantitatively remove TcO4 − in the presence of a large excess of NO3 − and SO4 2− . Decontamination experiments confirm that SCU‐102 represents the optimal Tc scavenger with the highest reported clean‐up efficiency, while first‐principle simulations reveal that the origin of the selectivity is the recognition of TcO4 − by the hydrophobic pockets of the structure.