Realizing ideal deuterium separation from isotopic mixtures
remains
a daunting challenge because of their almost identical sizes, shapes,
and physicochemical properties. Using the quantum sieving effect in
porous materials with suitable pore size and open metal sites (OMSs)
enables efficient hydrogen isotope separation. Herein, synthetic HKUST-1-derived
microporous mixed-valence Cu(I)Cu(II)-BTC (BTC = benzene-1,3,5-tricarboxylate),
featuring a unique network of distinct Cu(I) and Cu(II) coordination
sites, can remarkably boost the D2/H2 isotope
separation, which has a high selectivity (S
D2/H2
) of 37.9 at 30 K, in comparison with
HKUST-1 and other porous materials. Density functional theory (DFT)
calculations indicate that the introduction of Cu(I) macrocycles in
the framework decreases the pore size and further leads to relatively
enhanced interaction of H2/D2 molecules on Cu(II)
sites. The significantly enhanced selectivity of Cu(I)Cu(II)-BTC at
30 K can be mainly attributed to the synergistic effect of kinetic
quantum sieving (KQS) and chemical affinity quantum sieving (CAQS).
The results reveal that Cu(I) OMSs exhibit counterintuitive behaviors
and play a crucial role in tuning quantum sieving without a complex
structural design, which provides a deeper insight into quantum sieving
mechanisms and a new strategy for the intelligent design of highly
efficient isotope systems.
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