Ion exchange collaborating coordination substitution: More efficient Cr(VI) removal performance of a water-stable...

An unusual water-stable cationic metal-organic framework {[Cu(L)_0.5(bpe)(H₂O)](NO₃)•(H₂O)_0.5}_n (1) (H₄L = bis(3,5-dicarboxypyridinium)-p-xylylene) was synthesized, which was developed into an effective capture material for removal chromate from water. The results show that this material efficiently traps HCrO₄^- pollutant ions via single-crystal to single-crystal (SCSC) coordination substitution process. The HCrO₄^- uptake capacity of 1 is high to 190 mg/g. Meaningfully, the structure of 1-HCrO₄ ({[Cu(L)_0.5(bpe)(HCrO₄)]}_n) can be accurately obtained by single-crystal X-ray diffraction, where the chromate enter the framework to form stable coordination with central metal ions Cu²⁺. This is the first example of a stable coordination between chromate and the framework during the capture process. The captured HCrO₄^- are not dissociated easily into the solution due to the coordination bond. This interaction makes the enrichment of HCrO₄^- more stable and the capture capacity excellent. Furthermore, the HCrO₄^- releasing process displays good regeneration in a single crystal state, which further elaborates the reversible SCSC transformation. The mechanism of Cr(VI) removal was also confirmed by DFT calculation studies. This work provides a new way to design and develop efficient MOF capture materials.