“Shake ‘n Bake” Route to Functionalized Zr-UiO-66 Metal–Organic Frameworks

Abstract

We report a novel synthetic procedure for the high-yield synthesis of metal–organic frameworks (MOFs) with fcu topology with a UiO-66-like structure starting from a range of commercial Zr IV precursors and various substituted dicarboxylic linkers. The syntheses are carried out by grinding in a ball mill the starting reagents, namely, Zr salts and the dicarboxylic linkers, in the presence of a small amount of acetic acid and water (1 mL total volume for 1 mmol of each reagent), followed by incubation at either room temperature or 120 °C. Such a simple “shake ‘n bake” procedure, inspired by the solid-state reaction of inorganic materials, such as oxides, avoids the use of large amounts of solvents generally used for the syntheses of Zr-MOF. Acidity of the linkers and the amount of water are found to be crucial factors in affording materials of quality comparable to that of products obtained under solvo- or hydrothermal conditions.

Harvesting mechanical energy for hydrogen generation by piezoelectric metal–organic frameworks

“…S4, ESI †) than UiO-66 (3.03 nm and 0.28 cm 3 g À1 ). As reported in previous works on UiO-66-type MOFs, the surface areas and pore structures could be drastically changed after introducing ligands such as OH, COOH, NO 2 , NH 2 , Br and F. 35,36 This is because of the significant role of the polar properties of different ligands in the crystallization process. The extremely high surface area and porous structure of the asprepared piezoelectric MOFs overcome the disadvantage of conventional piezoelectric materials as catalysts.…”

Tailored Linker Defects in UiO-67 with High Ligand-to-Metal Charge Transfer toward Efficient Photoreduction of CO2

“…This result indicated that the absence of the linker caused the Zr–O cluster to form an electron-deficient state . The decrease of the binding energy of O–CO in O 1s for UiO-67-200 indicated that the electron cloud density of O decreased in the linkers . These results fully indicated that a certain degree of linker defects changed the coordination environment of Zr.…”

“…40 The decrease of the binding energy of O−CO in O 1s for UiO-67-200 indicated that the electron cloud density of O decreased in the linkers. 41 These results fully indicated that a certain degree of linker defects changed the coordination environment of Zr. The distributions of C, O, and Zr in all samples were also compared, as shown in Table S1.…”

Increased CO2 affinity and adsorption selectivity in MOF-801 fluorinated analogues

“…ZrTFS was prepared with a "Shake 'n Bake" procedure that we have previously employed for the synthesis of several UiO-66 MOF analogues. 54 In this procedure, a dense slurry of reagents in a small amount of a liquid is obtained instead of a clear solution upon a preliminary treatment using a ball mill. This probably induces a partial MOF crystallization before the heating stage, which provides a crystalline material at the end of the synthesis.…”