"Stereoscopic" 2D super-microporous phosphazene-based covalent organic framework: Design, synthesis and selective sorption towards uranium at high acidic condition.

So far, only five primary elements (C, H, O, N and B) and two types of spatial configuration (C2-C4, C6 and Td) are reported to build the monomers for synthesis of covalent organic frameworks (COFs), which have partially limited the route selection for accessing COFs with new topological structure and novel properties. Here, we reported the design and synthesis of a new "stereoscopic" 2D super-microporous phosphazene-based covalent organic framework (MPCOF) by using hexachorocyclotriphosphazene (a P-containing monomer in a C3-like spatial configuration) and p-phenylenediamine (a linker). The as-synthesized MPCOF shows high crystallinity, relatively high heat and acid stability and distinctive super-microporous structure with narrow pore-size distributions ranging from 1.0-2.1nm. The results of batch sorption experiments with a multi-ion solution containing 12 co-existing cations show that in the pH range of 1-2.5, MPCOF exhibits excellent separation efficiency for uranium with adsorption capacity more than 71mg/g and selectivity up to record-breaking 92%, and furthermore, an unreported sorption capacity (>50mg/g) and selectivity (>60%) were obtained under strong acidic condition (1M HNO3). Studies on sorption mechanism indicate that the uranium separation by MPCOF in acidic solution is realized mainly through both intra-particle diffusion and size-sieving effect.