Double-Walled Metal-Organic Framework with Regulable Pore Environments for Efficient Removal of Radioactive Cesium...

An anion double-walled metal-organic framework [Co₂Li₄(BTC)₃(DMF)(H₂O)·(CH₃)₂N] (1) based on heterobimetallic Li⁺ and Co²⁺ ions was successfully constructed. Utilizing selective destruction and formation of Co-O/Co-N bonds in the metal chains, [Co₂Li₄(BTC)₃(py)(H₂O)·(CH₃)₂N] (2) and [Co₂Li₄(BTC)₃(pi)(H₂O)·(CH₃)₂N] (3) with the same skeleton but distinct pore structures can be surprisingly obtained. Additionally, compounds 2 and 3 can be transformed into [Co₂Li₄(BTC)₃(H₂O)₂·(CH₃)₂N] (4) by soaking them in an ethanol solution. This kind of single-crystal-to-single-crystal transformation successfully regulates the pore structure of MOFs and enriches the diversity of the pore wall on the premise of retaining the original framework. Most impressively, compound 1 shows high adsorption capacity for Cs⁺ cations and is a good candidate to selectively accommodate Cs⁺ among the common alkali metal ions, which is future identified by single-crystal X-ray diffraction and inductively coupled plasma mass spectrometry (ICP-MS) test. Meanwhile, compound 1 can selectively adsorb methylene blue (MB) and crystal violet (CV) molecules over Rhodamine B (RMB).