Reticular Design of Precise Linker Installation into a Zirconium Metal–Organic Framework to Reinforce Hydrolytic Stability

Abstract

Reticular chemistry allows for the rational assembly of metal−organic frameworks (MOFs) with designed structures and desirable functionalities for advanced applications. However, it remains challenging to construct multi-component MOFs with unprecedented complexity and control through insertion of secondary or ternary linkers. Herein, we demonstrate that a Zr-based MOF, NU-600 with a (4,6)-connected she topology, has been judiciously selected to employ a linker installation strategy to precisely insert two linear linkers with different lengths into two crystallographically distinct pockets in a onepot, de novo reaction. We reveal that the hydrolytic stability of these linker-inserted MOFs can be remarkably reinforced by increasing the Zr 6 node connectivity, while maintaining comparable water uptake capacity and pore-filling pressure as the pristine NU-600. Furthermore, introducing hydrophilic −OH groups into the linear linker backbones to construct multivariate MOFs can effectively shift the porefilling step to lower partial pressures. This methodology demonstrates a powerful strategy to reinforce the structural stability of other MOF frameworks by increasing the connectivity of metal nodes, capable of encouraging developments in fundamental sciences and practical applications.

Highly Efficient Electrochemical Nitrate Reduction to Ammonia in Strong Acid Conditions with Fe2M‐Trinuclear‐Cluster Metal–Organic Frameworks

“…The above results indicate an excellent stability of Fe 2 M‐MOF‐based NO 3 RR catalysts that is superior to all the MOF‐based catalyst reported to date, which is also comparable to the state‐of‐the‐art inorganic NO 3 RR catalysts in general, but distinctively obtained in strong acidic electrolyte. The good acidic catalytic stability of Fe 2 Co‐MOF is probably due to the high connectivity between the polymetallic cluster and the ligand that is benefitial to the MOF stability [32, 35, 40, 41] . Overall, the optimal NH 3 yield rate of Fe 2 Co‐MOF reached to as high as 3463.3 μg h −1 mg −1 cat.…”

“…The good acidic catalytic stability of Fe 2 Co-MOF is probably due to the high connectivity between the polymetallic cluster and the ligand that is benefitial to the MOF stability. [32,35,40,41] Overall, the optimal NH 3 yield rate of Fe 2 Co-MOF reached to as high as 3463.3 μg h À 1 mg À 1 cat. , with the corresponding turnover frequency (TOF) up to 20653.5 μg h À 1 mg À 1 site at À 1.1 V RHE (the Fe 2 M clusters in MOF are considered as the active sites).…”

Tetra-Nuclear Cluster-Based Lanthanide Metal–Organic Frameworks as White Phosphor, Information Encryption, Self-Calibrating Thermometers, and Fe2+ Sensors

“…Each SBU contains two Eu 3+ , three deprotonated ligands of BTDB , one DMA, and one phen to form a neutral unit. The SBU tetra-nuclear cluster is connected in the oa and oc directions through coordination bonds to form a 2D MOF structure (Figure h). , The water contact angles of TbMOF (Figure S5a), EuMOF (Figure S5b), GdMOF (Figure S5c), and Tb,EuMOF (Figure S5d) slices were in the range of 91.7–95.3° (Table S2), which are a little larger than 90°; this may due to the fact that water can easily form hydrogen bonds with these LnMOFs. The coordinate bond lengths are in the normal range of 2.282–2.802 Å. − Other bond lengths and bond angles for the ligand of BTDB , TbMOF , EuMOF , and GdMOF are listed in Tables S4–S7, respectively.…”

“…The SBU tetra-nuclear cluster is connected in the oa and oc directions through coordination bonds to form a 2D MOF structure (Figure 1h). 31,32 The water contact angles of TbMOF (Figure S5a), EuMOF (Figure S5b), GdMOF (Figure S5c), and Tb,EuMOF (Figure S5d) slices were in the range of 91.7−95.3°(Table S2), which are a little larger than 90°; this may due to the fact that water can easily form hydrogen bonds with these LnMOFs. The coordinate bond lengths are in the normal range of 2.282−2.802 Å.…”

Anion-Induced Structural Transformation of a Cage-Based Metal–Organic Framework

“…We collected singlecomponent adsorption isotherms of Cu-TPA−BF 4 and Cu- Meanwhile, the peak at 2θ = 5.8°a fter adsorption can be barely observed, and the other peaks become wide as well (Figure 3). The above results indicate that Cu-TPA−BF 4 may not retain the pore structure after removing the solvent molecules, 48 which leads to a low adsorption quantity. By contrast, the N 2 uptake amount of Cu-TPA-SiF 6 can reach 362 cm 3 /g at 77 K and 1 bar.…”