Zhang Xinyue, Lei Xinying, Sun Hongfei, Ke Hanming, Xu Jingxuan, Yang Yuhao, Zhang Sai, Wen Tao, Ji Zhuoyu, Wang Xiangke
MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, P.R. China.
Beijing Key Laboratory of Environmental and Viral Oncology, College of Chemistry and Life Science, Beijing University of Technology, Beijing 100124, China.
Chem Bio Eng. 2024 Oct 19;2(1):53-63. doi: 10.1021/cbe.4c00141. eCollection 2025 Jan 23.
Emerging electrochemical uranium extraction from seawater offers a promising route for a sustainable fuel supply for nuclear reactor operation. In this work, we intentionally synthesized a conjugated microporous polymer (CMP) with π-conjugated skeletons and permanent porosity, which was induced by in situ electropolymerization on flexible carbon cloths, followed by postdecorating amidoxime groups to create functional materials (CMP-AO). Driven by an extra asymmetrical alternating current electrochemical extraction, the self-supporting and binder-free electrode is exceptionally capable of selectively and rapidly capturing U(VI) from simulated solution, affording an extraction capacity of ∼1806.4 mg/g without saturation. Experimental observation in combination with ex/in situ spectroscopy revealed that CMP-AO enabled surface selective binding sites (amidoxime groups) to U(VI), followed by electrocatalytic reduction (carbazole groups) to yield yellow precipitates (NaO(UO·HO) ) via reversible electron transfer in the presence of sodium electrolyte. Furthermore, the integrating adsorption-electrocatalysis system achieved an extraction capacity of 18.8 mg/g in real seawater for 21 days and good antibiofouling abilities, validating its feasibility for practical application.
新兴的从海水中电化学提取铀为核反应堆运行提供可持续燃料供应开辟了一条充满希望的途径。在这项工作中,我们特意合成了一种具有π共轭骨架和永久孔隙率的共轭微孔聚合物(CMP),它是通过在柔性碳布上原位电聚合,随后后修饰偕胺肟基团来制备功能材料(CMP-AO)。在额外的不对称交流电电化学提取的驱动下,这种自支撑且无粘结剂的电极能够从模拟溶液中选择性且快速地捕获U(VI),萃取容量约为1806.4 mg/g且不会饱和。结合实验观察与原位/非原位光谱表明,CMP-AO使表面选择性结合位点(偕胺肟基团)与U(VI)结合,随后进行电催化还原(咔唑基团),在钠电解质存在下通过可逆电子转移生成黄色沉淀(NaO(UO·HO) )。此外,集成吸附 - 电催化系统在实际海水中21天的萃取容量为18.8 mg/g,并且具有良好的抗生物污损能力,验证了其实际应用的可行性。