Department of Chemistry and Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720, United States; Chemical Sciences Division, Materials Sciences Division, and Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States.
Department of Chemistry and Department of Chemical and Biomolecular Engineering, University of California , Berkeley, California 94720, United States.
ACS Cent Sci. 2016 Apr 27;2(4):253-65. doi: 10.1021/acscentsci.6b00066. Epub 2016 Apr 12.
Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr(2+), Fe(3+), Nd(3+), and Am(3+), from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity.
多孔芳香骨架(PAFs)中含有高浓度的酸性官能团,具有分离镧系和锕系金属离子的特点,这是放射性废物处理所需要的。这些材料被证明可以无限期地耐受浓酸和强碱,可能允许进行多次吸附/解吸循环。此外,PAFs 结合了 MOFs 和无机/活性炭的特殊性质,产生可调孔径表面和最大的化学稳定性。在此,我们研究了一种碳基多孔芳香骨架 BPP-7(Berkeley 多孔聚合物-7)对水溶液中 Sr(2+)、Fe(3+)、Nd(3+)和 Am(3+)等金属离子的吸附。该材料显示出高的金属负载能力以及基于 Langmuir 吸附等温线和理想吸附溶液理论(IAST)计算的对锶的优异吸附选择性。部分基于 X 射线吸收光谱研究,发现 Nd(3+)的吸附更强是由于 BPP-7 高度交联和互贯的结构导致了多个金属离子和结合位点的相互作用。可回收性和可燃性实验表明,聚合物吸附容量的最小降解可以完成多次吸附/解吸循环。