Functional Carbon Capsules Supporting Ruthenium Nanoclusters for Efficient Electrocatalytic (99) TcO(4) (-) /ReO(4) (-) Removal from Acidic and Alkaline Nuclear Wastes.
Functional Carbon Capsules Supporting Ruthenium Nanoclusters for Efficient Electrocatalytic (99) TcO(4) (-) /ReO(4) (-) Removal from Acidic and Alkaline Nuclear Wastes.
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DOI：
10.1002/advs.202303536
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发表时间：
2023-10
期刊：
影响因子：
15.1
通讯作者：
Wang, Xiangke
中科院分区：
文献类型：
--
作者：
Liu, Xiaolu;Xie, Yinghui;Li, Yang;Hao, Mengjie;Chen, Zhongshan;Yang, Hui;Waterhouse, Geoffrey I. N.;Ma, Shengqian;Wang, Xiangke
从核废料中选择性地去除发射β的高铁酸根离子(99TcO4−)在技术上具有挑战性。提出了一种在高酸碱度、高离子强度和高辐射场的极端条件下选择性去除99TcO4−(或其替代物−)的实用方法。首先制备了负载Ru团簇的中空多孔掺氮碳胶囊(Ru@HNCC)，然后用含咪唑-N+单元的阳离子聚合物网络(R)对其进行修饰，以选择性结合99TcO4−和ReO4−。Ru@HNCC-R胶囊在广泛的条件下对99TcO4−/ReO4−具有很高的结合亲和力。然后，电化学氧化还原过程将吸附的REO_4−转化为块状REO_3，提供创纪录的高去除能力、快速的动力学和出色的长期耐用性，可以在3米HNO_3、模拟核废料-汉福德熔炉循环流和美国萨凡纳河遗址的碱性高放废物流中去除REO_4−(作为99TcO_4−的替代品)。原位拉曼光谱和X射线吸收光谱(XAS)分析表明，吸附的Re(VI)在Ru位上被电催化还原为Re(IV)O2中间体，然后再被氧化成难溶的Re(VI)O_3以便于收集。这种方法克服了在极端条件下选择性分离和去除99TcO4−/ReO4−的许多挑战，为核废物管理和环境修复提供了新的前景。支持Ru金属簇的中空碳胶囊和富含咪唑-N+单元的薄聚合物层使99TcO4−/ReO4−能够在与核燃料废物处理和储存相关的恶劣条件下高效去除。咪唑-N+促进了99TcO4−/ReO4−的选择性结合，而Ru团簇为99TcO4−/ReO4−的电催化转化提供了可逆的电子转移平台，从而产生了创纪录的高萃取效率。
The selective removal of the β‐emitting pertechnetate ion (99TcO4 −) from nuclear waste streams is technically challenging. Herein, a practical approach is proposed for the selective removal of 99TcO4 − (or its surrogate ReO4 −) under extreme conditions of high acidity, alkalinity, ionic strength, and radiation field. Hollow porous N‐doped carbon capsules loaded with ruthenium clusters (Ru@HNCC) are first prepared, then modified with a cationic polymeric network (R) containing imidazolium‐N+ units (Ru@HNCC‐R) for selective 99TcO4 − and ReO4 − binding. The Ru@HNCC‐R capsules offer high binding affinities for 99TcO4 −/ReO4 − under wide‐ranging conditions. An electrochemical redox process then transforms adsorbed ReO4 − to bulk ReO3, delivering record‐high removal capacities, fast kinetics, and excellent long‐term durability for removing ReO4 − (as a proxy for 99TcO4 −) in a 3 m HNO3, simulated nuclear waste‐Hanford melter recycle stream and an alkaline high‐level waste stream (HLW) at the U.S. Savannah River Site (SRS). In situ Raman and X‐ray absorption spectroscopy (XAS) analyses showed that adsorbed Re(VII) is electrocatalytically reduced on Ru sites to a Re(IV)O2 intermediate, which can then be re‐oxidized to insoluble Re(VI)O3 for facile collection. This approach overcomes many of the challenges associated with the selective separation and removal of 99TcO4 −/ReO4 − under extreme conditions, offering new vistas for nuclear waste management and environmental remediation. Hollow carbon capsules supporting ruthenium metal clusters and a thin polymer layer rich in imidazolium‐N+ units enable highly efficient 99TcO4 −/ReO4 − removal under harsh conditions relevant to nuclear fuel waste processing and storage. The imidazolium‐N+ promotes selective 99TcO4 −/ReO4 − binding, while the Ru clusters provide a reversible electron transfer platform for electrocatalytic conversion of 99TcO4 −/ReO4 − to TcO3/ReO3, resulting in record‐high extraction efficiencies.
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高效的电催化性铀从海水中提取，这是在N-C催化剂中启用的。
DOI：
10.1002/advs.202201735
发表时间：
2022-08
期刊：
Advanced science (Weinheim, Baden-Wurttemberg, Germany)
影响因子：
--
作者：
通讯作者：
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影响因子：
1.6
作者：
Choppin, GR;Morgenstern, A
通讯作者：
Morgenstern, A
影响因子：
11.4
作者：
Guo, Zizhang;Shams, Mehnaz;Lin, Yuehe
通讯作者：
Lin, Yuehe
影响因子：
11.2
作者：
Hao, Mengjie;Chen, Zhongshan;Ma, Shengqian
通讯作者：
Ma, Shengqian
影响因子：
56.7
作者：
Liu, Chong;Hsu, Po-Chun;Cui, Yi
通讯作者：
Cui, Yi