Zhao Yi-Ming, Sun Meng, Cheng Lin, Wang Kai-Yao, Liu Yang, Zhu Jia-Ying, Zhang Shun, Wang Cheng
Tianjin Key Laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials and Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, PR China.
College of Chemistry, Tianjin Normal University, Tianjin 300387, PR China.
J Hazard Mater. 2022 Mar 5;425:128007. doi: 10.1016/j.jhazmat.2021.128007. Epub 2021 Dec 7.
Removal of radioactive Ba, Co and Ni and their nonradioactive isotopes through ion exchange method would be highly beneficial for the safe disposal of liquid industrial waste, and it also bears importance for the emergency response to nuclear accident. Herein, we report the employment of an indium sulfide [CHCHNH]InS (InS-2) with exchangeable ethylammonium cations for efficient and selective uptake of Ba, Co and Ni. The corner-sharing linkage of P1-{InS} clusters in InS-2 endow the layered structure with nanoscale windows, which facilitates both transfer and accommodation of the large hydrated divalent metal ions. This results in ultrafast exchange kinetics (10-20 min) and top-level exchange capacities of 211.73 mg g for Ba, 103.57 mg g for Co, and 111.78 mg g for Ni. Particularly, InS-2 achieves ultrahigh K values of 2.3 × 10 mL g for Ba, 2.0 × 10 mL g for Co and 1.6 × 10 mL g for Ni, corresponding to remarkable removal efficiencies larger than 99.4% (C ~ 6 ppm). InS-2 shows high β and γ irradiation resistance, wide pH durability (pH 3-13 for Ba, pH 3-11 for Co and Ni), and outstanding selectivity against competitor ions (e.g. Na, K, Mg, Ca). The InS-2-filled ion exchange column exhibits a fantastic removal effect (R > 99%) for mixed Ba, Co, Ni, as well as Sr. The ultralong column-treatment on 20000 BVs of flow reveals an affinity order of Co > Ni > Ba > Sr for InS-2, which gives deep insights into the adsorption process and interaction between competitor ions. This excellent uptake of Ba (Ra by analogy), Co and Ni ions by InS-2 highlights the great potential of metal chalcogenides as a type of promising materials for minimizing contamination in complex wastewater.
通过离子交换法去除放射性钡、钴和镍及其非放射性同位素,对于液态工业废物的安全处置极为有益,对核事故应急响应也具有重要意义。在此,我们报道了使用具有可交换乙铵阳离子的硫化铟[CHCHNH]InS(InS-2)来高效、选择性地摄取钡、钴和镍。InS-2中P1-{InS}簇的角共享连接赋予层状结构纳米级窗口,这有利于大的水合二价金属离子的传输和容纳。这导致了超快的交换动力学(10 - 20分钟)以及钡的顶级交换容量为211.73毫克/克、钴为103.57毫克/克、镍为111.78毫克/克。特别地,InS-2对钡实现了2.3×10毫升/克的超高K值,对钴为2.0×10毫升/克,对镍为1.6×10毫升/克,对应着大于99.4%(C约6 ppm)的显著去除效率。InS-2表现出高的β和γ辐射抗性、宽的pH耐久性(钡为pH 3 - 13,钴和镍为pH 3 - 11)以及对竞争离子(如钠、钾、镁、钙)的出色选择性。填充InS-2的离子交换柱对混合的钡、钴、镍以及锶表现出出色的去除效果(R > 99%)。对20000床体积流量的超长柱处理揭示了InS-2对钴>镍>钡>锶的亲和顺序,这为吸附过程以及竞争离子之间的相互作用提供了深入见解。InS-2对钡(类推为镭)、钴和镍离子的这种出色摄取突出了金属硫属化物作为一类有前景的材料在减少复杂废水中污染方面的巨大潜力。