Ce-MIL-140: expanding the synthesis routes for cerium(iv) metal–organic frameworks

Abstract

A microwave-assisted synthesis method for Ce(IV)-based MOFs crystallizing in the MIL-140 structure has been developed. Three different linker molecules, i.e. terephthalic acid (H2BDC), 2-chloroterephthalic acid (H2BDC-Cl) and 2,6-naphtalenedicarboxylic acid (H2NDC)...

A Novel Cerium(IV)‐Based Metal‐Organic Framework for CO2 Chemical Fixation and Photocatalytic Overall Water Splitting

“…Furthermore, among these occurred Ce IV ‐MOFs, most of them have UiO‐66‐type architecture and thus their IBUs are dominated by the hexanuclear Ce−O clusters [7,8] . Very recently, several Ce IV ‐MOFs with MIL‐140 topology have been reported, in these frameworks the three‐dimensional (3D) network are constructed through the interconnection of the ligand molecules and the 1D IBU chains consisting of alternating edge sharing CeO 7 polyhedra [11,12] . To the best of our knowledge, this is the first IBU that is not based on the hexanuclear Ce−O cluster in Ce IV ‐MOFs.…”

“…[7,8] Very recently, several Ce IV -MOFs with MIL-140 topology have been reported, in these frameworks the three-dimensional (3D) network are constructed through the interconnection of the ligand molecules and the 1D IBU chains consisting of alternating edge sharing CeO 7 polyhedra. [11,12] To the best of our knowledge, this is the first IBU that is not based on the hexanuclear CeÀ O cluster in Ce IV -MOFs. Therefore, new synthetic routes to Ce IV -MOFs, particularly these with novel IBUs, are highly desirable for the development and the multifunctional applications of Ce IV -MOFs.…”

A unified topology approach to dot-, rod-, and sheet-MOFs

“…59 We see here an opportunity for new families of MOFs: for example, one candidate metal ion being Ce(IV), which we have shown here to be substantially stabilized compared with its aqueous solution chemistry. Ce(IV) MOFs are previously known, 46,[60][61][62][63][64][65][66][67][68][69][70][71][72] but it is not a large class of MOFs, possibly because of the use of Ce(IV) as a well-known oxidant in organic synthesis. However, Ce(IV) may be more stable than we think, 43,44 Figure 6.…”

Optimal Pore Chemistry in an Ultramicroporous Metal–Organic Framework for Benchmark Inverse CO2/C2H2 Separation

“…It is worth noting that Ce IV ‐MIL‐140‐4F exhibits a much higher electron cloud density on site I and more positive potentials on site II, compared to Zr IV ‐MIL‐140‐4F. This may originate from the strong electron‐withdrawing effect of Ce IV with empty and low‐lying 4f orbitals facilitating ligand‐to‐cluster charge transfer, and this process can be accelerated by the functionalization of ligands with electron‐withdrawing groups [12a,c,d, 15] . Compared with the molecular properties of C 2 H 2 and CO 2 , it is expected that these two specific and distinct sites with inverse electron potential in MIL‐140‐4F can well match the inverse quadrupole moments of C 2 H 2 and CO 2 .…”